HK1123031B

HK1123031B - Sun blocking stack

Info

Publication number: HK1123031B
Application number: HK09100135.7A
Authority: HK
Inventors: P．罗奎尼; A．埃克
Original assignee: 旭硝子欧洲玻璃公司
Priority date: 2005-05-11
Filing date: 2006-05-10
Publication date: 2013-12-13

Description

Sunlight-proof laminated structure

Technical Field

The present invention relates to a multilayer solar protection laminate structure (empilage) formed on a sheet of vitreous material, to a sheet of glass with said laminate structure, and to a multiple glazing (vitrage) comprising such a sheet of glass.

The invention relates to a solar control laminate comprising at least one functional layer based on a material that reflects infrared radiation and at least two dielectric coatings, one of which is a first dielectric coating deposited directly on a sheet of vitreous material, the other coating being located externally with respect to the functional layer or layers, each functional layer being surrounded by a dielectric coating. These different layers are deposited by magnetic field assisted reduced pressure cathode sputtering, for example in a well known magnetron type device.

Background

These solar-protection laminated structures are used to form solar-protection glazings with the aim of reducing the risk of excessive heating, for example caused by the sun in enclosed spaces with large glass surfaces, and thus reducing the electrical load for air conditioning in the summer. In this case, the glazing must pass the smallest possible amount of total solar radiation, i.e. it must have the lowest possible solar coefficient (FS or g). However, it is highly desirable to ensure a certain level of light Transmittance (TL) to provide a sufficient level of light inside the building. These somewhat conflicting requirements express the requirement to obtain a glazing unit with an improved selectivity (S), defined by the ratio of light transmittance to solar coefficient. These solar protection laminates also have low emissivity, which results in reduced heat loss through high wavelength infrared radiation. They thus improve the thermal insulation of large glass surfaces and reduce energy consumption and heating costs in cold seasons.

The light Transmission (TL) is the percentage of the incident luminous flux of the light source D65 transmitted through the glazing. The solar coefficient (FS or g) is the percentage of incident energy radiation that is directly transmitted by the glazing and absorbed by it and then radiated in the opposite direction to the energy source relative to the glazing.

These solar-protection glazing units are usually assembled as double glazing units, in which a glass sheet with a laminated structure is joined to another glass sheet with or without a coating, wherein the multilayer laminated structure is located in the space between the two glass sheets.

In some cases, it is often necessary to subject the glazing to a mechanical reinforcing operation, such as thermal tempering (trempe) of the glass sheets, with the aim of improving its resistance to mechanical stresses. In the manufacturing and shaping processes of glazing units, performing these tempering operations on an already coated substrate has several advantages over coating an already treated substrate. These operations are carried out at relatively elevated temperatures (which refers to temperatures at which, for example, a silver-based ir-reflecting layer tends to deteriorate and lose its optical properties and its properties with respect to ir-radiation). Therefore, in the case where the coated glass sheet must be subjected to a thermal tempering operation, quite special precautions must be taken to form a laminated structure capable of undergoing a thermal tempering or bending process without losing its optical and/or energy-related properties, hereinafter often referred to by the term "temperable".

It is also desirable that the glazing unit meet certain aesthetic criteria in terms of light Reflectance (RL), which is the percentage of the incident light flux from light source D65 that is reflected by the glazing, as well as reflected and transmitted color. The market demands glazing with low light reflectivity. The combination of high selectivity and low light reflectance sometimes results in the formation of a purple hue in the reflection, which has very little aesthetic appeal.

To reduce the amount of heat that penetrates the glazing into the site, the invisible infrared thermal radiation is prevented from penetrating the glazing by reflecting it. This is the function served by the functional layer or layers based on a material that reflects infrared radiation. This is an essential element in solar-protection laminated structures. However, visible radiation also transmits a substantial portion of the thermal radiation. In order to reduce the transmission of this part of the thermal radiation and in addition to eliminating the energy supplied by the infrared radiation, the degree of light transmission must also be reduced.

The solution proposed in patent application WO 02/48065 a1 is to insert an absorber layer, for example a TiN absorber layer, in a laminated structure and to enclose this layer between two layers of transparent dielectric material. Thus, this document explains that the absorbing layer is not in contact with the glass, which limits the problems associated with the diffusion of oxygen and alkaline substances from the glass, in particular under the effect of heat when the glass has to be subjected to a heat treatment; the absorption layer is also not in contact with silver, which limits the problem of deterioration of the silver layer caused by oxidation of the absorption layer upon contact, in particular under the action of heat.

One of the problems directly resulting from the just mentioned situation is that the absorption layer in some cases, in particular during heat treatment, oxidizes and becomes more transparent, whereby the reason for its incorporation in the laminated structure is partly lost. Furthermore, the degree of oxidation of the absorber layer will depend on the heat treatment conditions, which means that it will be difficult to maintain the properties of the laminated structure after tempering. To limit this effect, the above document proposes to encapsulate the absorber layer between two layers of silicon nitride or aluminum nitride.

Apart from the fact that the results are not entirely satisfactory, the solution proposed in this document has the disadvantage of making the laminated structure, which is already complex in nature, somewhat more complex. In particular, this solution requires the use of a specific deposition area with a conditioned atmosphere right in the middle of a given dielectric in order to deposit the absorber layer. Another drawback of the solution proposed in this document WO' 065 is that it is difficult to neutralize the tint provided by the absorbing layer interposed between the dielectrics.

Disclosure of Invention

The invention relates to a multilayer solar protection laminate structure formed on a sheet of vitreous material, comprising at least one functional layer comprising a silver-based material reflecting infrared radiation and at least two dielectric coatings, one of which is a first dielectric coating deposited directly on the sheet of vitreous material, the other coating being located externally with respect to the functional layer or layers, each functional layer being surrounded by a dielectric coating, wherein the laminate structure, when deposited on a sheet of ordinary transparent soda-lime float glass 6 mm thick, has a solar coefficient FS of less than 45% and a light transmission TL of less than 70%, characterized in that the laminate structure comprises a substantially metallic absorbing material placed next to the functional layer or contained within such a functional layer, the material being based on at least one of the following elements: pd, Pt, Au, Ir, Rh, Ru, Os, Co, Ni, Cu, Cr, La, Ce, Pr, Nd, W, Si, Zn, Mo, Mn, Ti, V, Nb, Hf, Ta, and alloys thereof.

The term "absorbing material" is understood to mean a material that absorbs a portion of the visible radiation, whose spectral absorption index k (λ) is on average higher than 1.9, said average being calculated from three points of the visible spectrum located at 380, 580 and 780 nm. The values of the spectral absorption indices are given in the Handbook of Chemistry and Physics, 70 th edition, CRC Press, 1989-.

The absorbent material used in the present invention is substantially in metallic form. The material may also optionally be doped with elements other than those listed, such as aluminum or boron, for various reasons, particularly for ease of deposition in magnetron devices or ease of machining the target.

It is known that silicon should be properly classified as a semi-metal, but since silicon behaves like some metals in all respects, it is included in the term "substantially metallic absorbing material" in the present invention for the sake of simplicity.

The term "in close proximity" means that the absorbing material forms part of a layer which is placed in direct contact with the functional layer or is possibly separated from the functional layer by a very thin sacrificial metal layer having a tendency to absorb oxygen or metal suboxides. Since the absorption material is placed next to the functional layer or is contained in such a functional layer, it therefore has a favorable effect on the reflection of infrared radiation and also benefits from the measures of protection against oxidation of the material used for reflecting infrared radiation.

The invention relates in particular to a laminated structure having a solar coefficient FS of less than 45%, in particular 20 to 45%, and a light transmittance TL of less than 70%, in particular 30 to 70%, when deposited on a sheet of ordinary transparent soda-lime float glass of 6 mm thickness. Under these conditions, they preferably have a solar coefficient FS of 25 to 40% and a light transmission TL of 35 to 68%.

It has surprisingly been found that when forming the layered structure of the present invention, the absorption level of the layered structure can be easily determined and maintained even under particularly harsh conditions, such as heat treating the layered structure, and still achieve the desired optical and aesthetic appearance, such as a reflectively neutral (neutral) appearance.

The chosen absorbent material plays a fundamental role in the achievement of this result. At least some of these materials, in particular palladium and platinum, have been known, for example from document EP 543077 a1, as their effect of improving the resistance of the laminated structure to humidity and chemical attack, either as an alloy with an infrared reflecting layer, in particular silver, or as an alloy with a sacrificial metal layer on silver. It is concerned with forming a laminated structure having the highest possible light transmittance. The use of these materials to regulate the degree of endotherm in visible radiation is entirely new and differs from the indications given hereinbefore. Furthermore, they are relatively expensive materials, and their use as absorbent materials in continuous production is surprising. We have found that the present invention surprisingly provides a truly significant advantage in terms of the adjustment of the solar coefficient of a glazing (low solar coefficient of less than 45% in the case of a single glazing) and high selectivity. Furthermore, the selected absorbing material may additionally contribute to the reflection of infrared radiation.

Dielectric coatings are well known in the art of layers deposited by cathodic sputtering. There are many suitable materials, and there is no need to list them here. They are usually metal oxides, oxynitrides or nitrides. For example, the following may be mentioned as some of the most common: TiO 2₂、SnO₂、ZnO、Si₃N₄、AlN、Al₂O₃、ZrO₂、Nb₂O₅And Bi₂O₃. For the outer coating, SnO can be added if the laminated structure does not have to be subjected to high temperature heat treatment₂Are particularly suitable dielectric materials.

External interface of laminated structureThe electrocoat preferably comprises at least one zinc-tin mixed oxide base layer containing at least 20% tin and/or an oxygen diffusion barrier layer having a thickness greater than 5 nanometers selected from the group consisting of: AlN, AlNxOy, Si₃N₄、SiOxNy、SiO₂ZrN, SiC, SiOxCy, TaC, TiN, TiNxOy, TiC, CrC, DLC, and alloys thereof, and nitrides or oxynitrides of the alloys such as SiAlOxNy or SiTixNy. The outer dielectric thus defined is beneficial for the stability of the absorbing material, in particular when the laminated structure is subjected to various chemical and thermal attacks from the outside, in particular during high temperature heat treatments such as bending and/or tempering.

"DLC" is an abbreviation of the well-known term "diamond-like carbon" which refers to a carbon-based layer having tetrahedral bonds similar to diamond.

According to the first aspect of the invention, the absorbent material is preferably comprised in a functional layer. Advantageously, the functional layer contains from 1 to 30 atomic%, preferably from 5 to 20%, of an absorbing material, which is an alloy with or doped by a silver-based material that reflects infrared radiation. The absorbing material may be deposited by sputtering using a cathode formed of an alloy with a material that reflects infrared radiation. For example, a cathode of silver doped or alloyed with an amount (e.g. 1 to 20%, preferably 5 to 20%) of an absorbing material (e.g. palladium or platinum) may be used. It is also possible to use two cathodes, for example a silver cathode and a palladium cathode, which are co-sputtered onto a sheet of vitreous material. This results in a functional layer based on a material which reflects infrared radiation and which contains an absorbing material.

Preferably, the functional layer contains 5 to 10% of the absorbent material. It has been found that such a ratio enables a good compromise to be achieved between the absorption level brought about by the absorbing material and the infrared-reflecting properties of the base material of the functional layer.

The functional layer may for example comprise at least one of the following elements: ti, Zn, Mo, Mn, Nb, V or Hf. These elements can in particular produce absorption defects (resorufsabsorbants) in the functional layer, which are beneficial for reducing the solar coefficient.

Preferably, according to a preferred embodiment of the first aspect of the present invention, the absorbent material contained in the functional layer is selected from the following materials: ni, Cr, NiCr, CoCr, W, Si and NiV. We have in fact found that in this aspect of the invention these materials form a particularly advantageous combination with silver-based materials that reflect infrared radiation. These combinations particularly form a non-temperable/bendable daylight-blocking laminate structure with a low daylight factor, which has a reflective and transmissive hue from neutral to bluish, which has an aesthetically pleasing appearance. The elements Ni, Cr, NiCr, CoCr, W, Si and NiV, in particular NiCr and CoCr, are particularly advantageously used to form a solar-protected sandwich structure which is light blue-grey in transmission and reflection without having to be subjected to a high-temperature heat treatment.

Preferably, according to another preferred embodiment of the first aspect of the present invention, the absorbent material contained in the functional layer is selected from the following materials: os, Co, Pd, Pt, Ir, Ru and Rh. These materials are advantageously used to form solar control laminates that are heat treated. It has been found that they readily retain their absorption characteristics and provide a laminated structure having pleasing transmitted and reflected hues after heat treatment of the glazing.

Nickel and cobalt are particularly magnetic elements that present certain deposition problems in magnetron-type cathode sputtering devices. However, there is no problem if they are used as dopants for infrared-reflective materials, for example in silver in a proportion of 5%.

Preferably, according to this first aspect of the invention, the functional layer contains from 1 to 30% by atom, advantageously from 5 to 20%, of an absorbing material chosen from Pd, Pt, Au, Ir, Rh, Ru, Os, Co, La, Ce, Pr, Nd and alloys thereof, and the outer dielectric coating of the laminated structure comprises at least one zinc-tin mixed oxide based layer containing at least 20% tin and/or an oxygen diffusion barrier layer having a thickness greater than 5 nm chosen from: AlN, AlNxOy, Si₃N₄、SiOxNy、SiO₂ZrN, SiC, SiOxCy, TaC, TiN, TiNxOy, TiC, CrC, DLC, and alloys thereofAnd nitrides or oxynitrides of alloys such as SiAlOxNy or SiTixNy. This feature makes it possible to easily obtain a solar-protected laminated structure suitable for high-temperature heat treatment and maintaining their absorption characteristics after heat treatment.

According to the second aspect of the invention, the absorbing material preferably at least partly constitutes a part of a separate layer deposited below or above and in direct contact with the functional layer. With this arrangement, the risk of a reduction in the infrared radiation reflection properties of the functional layer is reduced, in particular in the case of a high proportion of absorbing material.

According to a first preferred embodiment of this second aspect of the invention, the getter material is preferably incorporated, by doping or alloying, into a sacrificial metal layer for protecting the functional layer against chemical attack (in particular against oxidation), for example a titanium layer containing about 5 atomic% of palladium. Again, this layer may be formed by a cathode of an alloy of the sacrificial metal and the absorbing material, or by co-sputtering of two separate cathodes. The sacrificial metal layer preferably contains 5 to 20% of an absorbing material.

According to a second preferred embodiment of the second aspect of the present invention, the absorbent material preferably constitutes the main part of a separate layer deposited below or above and in direct contact with the functional layer. Thus, the functional layer may be deposited directly onto the absorber layer or the absorber layer may be deposited directly onto the functional layer. It has been found that such an arrangement is beneficial in terms of the performance imparted to the laminated structure and in terms of ease of industrial use. This is because the absorber material deposited in metallic form is easily incorporated into the substantially metallic type deposition area of the functional layer without complicating the deposition process. On the other hand, among the absorbing materials listed within the scope of the present invention, it is easy to find materials compatible with the silver-based materials used, which reflect infrared radiation.

It has been found that, for example, by using the alloy CoCr in the form of a separate absorption layer deposited onto the functional layer, a non-temperable solar laminate structure can be easily obtained having a low solar coefficient and an aesthetically acceptable general appearance, in particular a bluish-grey appearance in transmission and reflection, which is particularly pleasant and meets market requirements.

Preferably, according to a second preferred embodiment of the second aspect of the present invention, the absorbing material is selected from Pd, Pt, Au, Ir, Rh, Ru, Os, Co, La, Pr, Nd and alloys thereof, and the outer dielectric coating of the laminated structure comprises at least one zinc-tin mixed oxide based layer containing at least 20% tin and/or an oxygen diffusion barrier layer having a thickness greater than 5 nm selected from: AlN, AlNxOy, Si₃N₄、SiOxNy、SiO₂ZrN, SiC, SiOxCy, TaC, TiN, TiNxOy, TiC, CrC, DLC and their alloys, and nitrides or oxynitrides of alloys, such as SiAlOxNy or SiTixNy. The combination of these absorbing materials with the outer dielectric coating thus defined helps to determine the desired absorption level of the solar protection laminate after high temperature heat treatment.

Preferably, such a separate layer of absorbing material has a physical thickness of 0.3 to 10 nm, advantageously 0.4 to 5 nm, ideally 0.8 to 3 nm. These thickness ranges enable to obtain a solar-protection glazing unit having a low solar coefficient and a high selectivity and an aesthetic appearance that meets market requirements.

Advantageously, the absorbing material is chosen from at least one of the following elements: pt, Pd, Co, Ir, Ru, Rh, Os, CoCr, Ti, and NiCr and alloys thereof. These absorbent materials are capable of forming an effective solar-protection laminate structure with a desirable aesthetic appearance, particularly when they are provided in a layer separate from the functional layer. The last three elements mentioned, namely CoCr, Ti and NiCr, are more particularly used for a laminated structure which does not have to be subjected to a high temperature heat treatment.

Preferably, according to both aspects of the invention and any embodiment of these aspects of the invention, the absorbing material is palladium. Within the scope of the present invention, this association with the silver-based functional layer makes it possible to obtain a selective solar control laminate structure having high corrosion resistance and easily maintaining its absorption properties.

Preferably, from 4 to 35%, advantageously from 8 to 22%, of the light absorption of the layered structure is attributable to the absorbing material. A solar factor sufficient for a product that meets market requirements is thereby obtained.

Preferably, the first dielectric coating and the outer dielectric coating comprise at least one layer of a zinc-tin mixed oxide containing at least 20% tin. It has been found that such a structure enhances the resistance of the laminated structure to heat treatment.

Advantageously, the laminated structure comprises, in order starting from a sheet of vitreous material, at least the following sequence of layers:

a) a first dielectric coating layer is formed on the substrate,

b) a silver-based functional layer,

c) an absorption layer is arranged on the outer surface of the substrate,

d) optionally, one or two layers of optionally suboxidised sacrificial metal selected from one or more of the following materials: ti, Ni, Cr, Nb, Zn, Zr, Al, Ta and alloys thereof,

e) an outer dielectric layer.

It has been found that this particular hierarchical order is advantageous in maintaining the absorption properties of the laminated structure, particularly during heat treatment.

The optional sacrificial metal layer may be comprised of a bilayer, such as NiCr/Ti. Such bilayers are the subject of patent application WO 03/106363A 2, filed in the name of the applicant and published 24/12/2003, the contents of which are incorporated herein by reference.

In order to obtain a high-performance selective solar-protection laminate structure, it is advantageous to include at least two functional layers separated by at least one intermediate dielectric coating.

Preferably, the absorbent material is placed or contained in the functional layer immediately adjacent to the functional layer furthest from the sheet of vitreous material and the hue does not change significantly when the absorbent material is exchanged for another absorbent material providing the same level of absorption. By combining the specific arrangement of the absorbent layer, in particular when it is located on or contained in the second functional layer, with a reasonable choice of dielectric structure, a laminated structure can be obtained which is independent of the elements constituting the absorbent material. It is therefore easier to select a material that is easier to deposit by cathodic sputtering or a less expensive material without allowing the experienced observer to easily see the change in hue by visual inspection and without changing the solar coefficient by more than 1%. In this case, for example, when the laminated structure does not have to be subjected to heat treatment, palladium may be replaced with titanium or NiCr without significantly changing the color tone of the laminated structure. However, it is of course necessary to adjust the thickness of the absorbing layer or the percentage of absorbing material in the alloy of absorbing material and functional layer or sacrificial layer to obtain the same absorption level, depending on the nature of the absorbing material. It is convenient to exchange one absorbent material for another, for example for reasons of cost, production considerations or other reasons, since it is sufficient to adjust the thickness in accordance with the absorption level and to achieve directly the correct hue of the laminate structure.

Preferably, the laminated structure comprises, in order starting from a sheet of vitreous material, at least the following sequence of layers:

a) a first dielectric coating layer is formed on the substrate,

b) a first silver-based functional layer having a first silver-based functional layer,

c) one or two layers of sacrificial metals, optionally under-oxidised, selected from one or more of the following materials: ti, Ni, Cr, Nb, Zn, Zr, Al, Ta and alloys thereof,

d) an intermediate dielectric coating layer is formed on the substrate,

e) a second silver-based functional layer,

f) an absorption layer is arranged on the outer surface of the substrate,

g) optionally, one or two layers of optionally suboxidised sacrificial metal selected from one or more of the following materials: ti, Ni, Cr, Nb, Zn, Zr, Al, Ta and alloys thereof,

h) an outer dielectric layer.

By using, for example, a palladium absorption layer, a sacrificial metal layer of low-oxidation NiCr in the form of NiCrOx and Si₃N₄Can be easily formed into a laminated structure whose optical properties are not altered by high temperature heat treatment operations of the toughening and/or bending type, that is to say that a glass sheet coated and subsequently toughened can be placed next to a glass sheet with the same laminated structure but without heat treatment, because it has the same aesthetic appearance. The absorption capacity imparted to the laminated structure by palladium is not altered by the heat treatment.

Advantageously, when silver is used as the infrared reflective material, a zinc oxide-based or low zinc oxide-based layer, optionally doped with, for example, aluminum, is placed under each silver layer in direct contact therewith. This combination is particularly beneficial in terms of the corrosion resistance of silver.

a) a first dielectric coating comprising at least one zinc-tin mixed oxide base layer,

d) an intermediate dielectric coating layer is formed on the substrate,

e) a second silver-based functional layer,

f) a palladium-based absorption layer,

h) an outer dielectric coating comprising at least one zinc-tin mixed oxide based layer.

Advantageously, all dielectric coatings comprise a zinc-tin mixed oxide base layer containing approximately 50% tin and zinc, and a zinc-tin mixed oxide base layer containing not more than approximately 10% tin and at least approximately 90% zinc, this latter layer each being arranged closer to the following functional layer than the mixed oxide layer containing approximately 50% tin. It has been found that this arrangement enables to obtain a solar control laminate structure with a low solar factor and a high selectivity, which has excellent corrosion resistance and is easily subjected to high temperature heat treatment without losing its absorption properties and without losing its infrared reflection properties. This structure also makes it possible to easily obtain a laminated structure having a neutral reflection hue.

The laminated structure is advantageously composed of SiO in a thickness of 1.5-10 nm₂Or a protective layer of the final SiC film. In the case of a laminated structure suitable for high-temperature heat treatment, the protective layer is advantageously constituted by a TiN film which oxidizes during the heat treatment to form TiO₂Followed by SiO₂Or a final film of SiC.

Preferably, the laminated structure ends with a thin carbon-based protective layer having a thickness of 1.5-10 nm. Such protective layers, which are sputter deposited from a carbon target in a neutral atmosphere, are well suited for protecting the laminated structure during handling, transport and storage prior to heat treatment. With regard to the use of carbon, such a protective layer burns during the high temperature heat treatment and disappears completely from the final product.

The invention extends to a glass sheet with a laminated structure as defined above.

Preferably, such a glass sheet has a hue tested on glass side reflection represented by L x, -4 to +3, advantageously-2.5 to +1.5, and b x-4 to-16, advantageously-6 to-13, of from 30 to 55, advantageously 40 to 50.

Preferably, this glass sheet is subjected to a tempering and/or bending heat treatment after the deposition of the multilayer laminated structure.

Preferably, the light absorption of 4 to 35%, preferably 8 to 22%, of the laminated structure after heat treatment is attributable to the absorbing material. The invention makes it possible in particular to obtain a glazing with a relatively high level of absorption and an aesthetic appearance after heat treatment.

The invention also extends to an assembly (ensemble) formed of a first group comprising at least one glass sheet according to the invention which has been subjected to a high-temperature heat treatment and a second group comprising at least one glass sheet according to the invention which has not been subjected to a high-temperature heat treatment, characterized in that the two groups have a similar visual appearance of reflection on the glass side, so that they can be juxtaposed without significant visual differences.

The invention also extends to a multiple glazing unit, in particular a double glazing unit, comprising a glass sheet with a laminated structure as defined above, with or without tempering and/or bending heat treatment after deposition of the multilayer laminated structure.

Preferably, the multiple glazing of the invention has a solar factor FS of from 15 to 40%, a light transmission of at least 30% and a relatively neutral transmission color and a neutral to bluish reflection color on the side of the glass sheet with the laminated structure. Preferably, the multiple glazing of the invention has a solar coefficient FS of 20 to 35%, advantageously 25 to 35%, and a light transmission of at least 45%, advantageously at least 50%, ideally at least 55%. Such multiple glazing has particularly beneficial solar control properties relative to its higher light transmission, while still having an aesthetic appearance that makes it easy to integrate into building assemblies.

Preferably, the multiple glazing has, on the side of the glass sheet with the laminated structure, a reflection tint represented by L from 40 to 55, preferably from 45 to 52, a from 1.5 to-6, preferably from 0.5 to-4, and b from-3 to-15, preferably from-5 to-12, wherein the laminated structure is placed towards the inner space of the multiple glazing.

Detailed Description

The invention will now be described in more detail by way of the following preferred examples, without being limited thereto.

Examples

Example 1

A common clear soda-lime float glass plate of 2 m x 1 m x 6 mm thickness was mounted in a magnetron-type cathode sputtering apparatus operated under reduced pressure (about 0.3Pa) with the aid of a magnetic field. Depositing on the glass sheet a multilayer solar control laminate structure comprising in order:

a) a first dielectric coating, consisting of two oxide layers, which are deposited from zinc-tin alloy cathodes with different compositions in a reactive atmosphere formed by a mixture of argon and oxygen. A first zinc-tin mixed oxide having a thickness of about 30 nm is formed from a cathode of a zinc-tin alloy having 52 wt.% zinc and 48 wt.% tin to form zinc stannate Zn₂SnO₄The spinel structure of (1). A second zinc-tin mixed oxide ZnSnO having a thickness of about 10 nm_xDeposited from a zinc-tin alloy target having 90 wt.% zinc and 10 wt.% tin.

b) A first infrared-reflective functional layer consisting of about 11 nanometers of silver from an almost pure silver target in a neutral argon atmosphere,

c) a first sacrificial metal bilayer consisting of a first NiCr layer deposited from an alloy target with 80% Ni and 20% Cr, with a thickness of 1 nm, and a second Ti layer deposited from a titanium target, with a thickness of 2.5 nm. These layers were all deposited in a slightly oxygen contaminated argon stream from the adjacent chamber. It should be noted that the plasma oxidizing atmosphere completely oxidizes the titanium layer during the deposition of the next layer described below, so that at the end of the second dielectric deposition process, the titanium is almost completely oxidized to form dense TiO₂And (3) a layer. Alternatively, a layer in the form of partially oxidized TiOx may also be deposited. The layer may also be deposited, for example, from a TiOx ceramic target in an Ar atmosphere containing a small proportion of oxygen to maintain the TiOx sufficiently oxidized to make it transparent. It can also be used for plasma oxidation for deposition of the next layer.

d) Second dielectricCoating consisting of two zinc-tin mixed oxide layers deposited from cathodes of zinc-tin alloys with different compositions in a reactive atmosphere formed by a mixture of oxygen and argon. A first zinc-tin mixed oxide having a thickness of about 77 nm was deposited from a metal target of a ZnSn alloy having 52 wt% Zn and 48 wt% Sn to form zinc stannate Zn₂SnO₄The spinel structure of (1). Second zinc-tin mixed oxide ZnSnO with a thickness of about 13 nm_xDeposited from a ZnSn alloy target having 90 wt% Zn and 10 wt% Sn.

e) A second infrared reflective functional layer consisting of about 18 nanometers of silver from an almost pure silver target in a neutral argon atmosphere.

f) A layer of absorbing material consisting of about 1 nanometer palladium from a palladium target in the same neutral argon atmosphere as layer e).

g) The second sacrificial metal bilayer, in the same way as the first sacrificial metal bilayer described above, is composed of a first 1 nm NiCr layer covered by a second 2.5 nm Ti layer.

h) The third dielectric coating, the outer dielectric coating, consists of two oxide layers, which are deposited from cathodes of zinc-tin alloys with different compositions in a reactive atmosphere formed by a mixture of oxygen and argon. First zinc-tin mixed oxide ZnSnO having a thickness of about 7 nm_xDeposited from a metal target of a ZnSn alloy having 90 wt% Zn and 10 wt% Sn. A second zinc-tin mixed oxide having a thickness of about 17 nm was deposited from a ZnSn alloy target having 52 wt% Zn and 48 wt% Sn to form zinc stannate Zn₂SnO₄The spinel structure of (1).

i) The stacked structure was then completed by depositing a 5 nm thick protective layer of TiN from titanium palladium in a nitrogen atmosphere.

It should be noted that all ZnSnO_xThe layer is sufficiently oxidized to be as transparent as possible. It should also be noted that the thickness of Ti, TiOx and TiN are in TiO₂The equivalent thickness (i.e. as a result of oxidation of Ti, TiOx or TiN) is given inThe state in the finished product after the heat treatment, and for Ti already even in the intermediate glazing suitable for the heat treatment.

The glass sheet, which was just coated with the multilayer solar control laminate structure, had the following properties upon exiting the layer deposition apparatus:

TL 51.1%; FS 32.5% epsilon (emissivity) 0.025; the absorption rate was 34.5%, of which approximately 10% was attributable to the palladium layer of the absorbent material;

the transmitted hue is represented by the following value:

L*＝71.5；a*＝-3.9；b*＝+3.5

the reflected hue on the glass side is represented by the following value:

RL＝14.5％；L*＝45.5；a*＝-10.0；b*＝-15.8；λ_d478 nm; purity 30.7%.

In the present invention, the following common terms are used for measured values or calculated values. The light Transmittance (TL), light Reflectance (RL), light Absorption (AL) (percentage of the luminous flux of light source D65 absorbed by the glazing) and transmitted hue (1976 CIELAB value L a b) were determined with light source D65/2 °. Regarding the reflected color tone, 1976 CIELAB value (L a b) and dominant wavelength (λ a)_d) And purity (p) was measured using illuminant D65/10 ℃. The solar coefficient (FS or g) is calculated according to the standard EN 410. The values U (coefficient k) and emissivity (epsilon) are calculated according to the standards EN673 and ISO 10292.

The coated glazing with the multilayer solar-protection laminate formed on a glass sheet was then subjected to a hot tempering operation, during which it was exposed to a temperature of 690 ℃ for 6 minutes and subsequently quenched with a cold air jet. During this heat treatment, the NiCr film of the barrier layer is sufficiently oxidized to be transparent, while also forming an effective and stable shield to protect the silver layer. The TiN upper protective layer is oxidized into TiO₂。

After this treatment, the coated and tempered glazing had the following properties:

TL 68.1%; epsilon (emissivity) 0.023; rs 1.6 Ω/sq.; the absorption rate was 21.2%, of which approximately 10% was attributable to the palladium layer of the absorbent material;

the transmitted hue is represented by the following value:

l ═ 86.1; a ═ 2.0; b ═ 1.2; turbidity 0.09%;

the reflected hue on the glass side is represented by the following value:

RL＝10.6％；L*＝39.3；a*＝-2.1；b*＝-12.1；λ_D＝474nm；p＝22.1％。

haze values are defined as% values obtained by multiplying the ratio of diffuse light transmission to total light transmission by 100. This value is measured according to the standard ASTM D1003.

It was found that the absorption value generated by the absorption layer does not decrease after the high temperature heat treatment.

This coated glazing was then assembled with another 6 mm clear glass sheet into a double glazing, with the coating on the interior space side of the double glazing. The gap between the two sheets was 15 mm and the air therein was replaced by argon. When the double glazing is viewed on the glass side of the coated glazing with the laminate in position 2, i.e. when viewed from the glass side, the glazing with the laminate is seen first and then the clear glass sheet without the layer is seen, the following properties are noted:

TL is 61.7%; RL ═ 14.4%; FS is 36.5%; 1.7 value of S1.05W/(m)²·K)；

The transmitted hue is represented by the following value:

L*＝82.8；a*＝-2.9；b*＝+1.4

the reflected hue is represented by the following value:

L*＝45.0；a*＝-2.5；b*＝-9.9；λ_D＝475nm；p＝17.1％。

visual inspection in the reflection of a double glazing shows a uniform tint and appearance across the surface. The invention enables the formation of a double glazing with a low solar coefficient, which maintains a sufficient light transmission and has a very high aesthetic appeal.

Example 2

Example 2 was carried out in the same manner as example 1 but with a different laminated structure. In this example, the following sequence was used:

a) a first dielectric coating consisting of two oxide layers deposited from zinc-tin alloy cathodes having different compositions in a reactive atmosphere formed by a mixture of argon and oxygen. A first zinc-tin mixed oxide having a thickness of about 24 nm is formed from a cathode of a zinc-tin alloy having 52 wt.% zinc and 48 wt.% tin to form zinc stannate Zn₂SnO₄The spinel structure of (1). A second zinc-tin mixed oxide ZnSnO having a thickness of about 8nm_xDeposited from a zinc-tin alloy target having 90 wt.% zinc and 10 wt.% tin.

b) A first infrared-reflective functional layer consisting of about 9 nanometers of silver from an almost pure silver target in a neutral argon atmosphere,

c) a first sacrificial metal layer consisting of a Ti layer deposited from titanium palladium with a thickness of 5 nm. This layer was deposited in a stream of argon slightly contaminated with oxygen from the adjacent chamber. It should be noted that the plasma oxidizing atmosphere only partially oxidizes the titanium layer during the deposition of the next layer described below.

d) A second dielectric coating consisting of two zinc-tin mixed oxide layers deposited from zinc-tin alloy cathodes of different compositions in a reactive atmosphere formed by a mixture of oxygen and argon. A first zinc-tin mixed oxide having a thickness of approximately 65 nm was deposited from a metal target of a ZnSn alloy having 52 wt.% Zn and 48 wt.% Sn to form zinc stannate Zn₂SnO₄The spinel structure of (1). A second zinc-tin mixed oxide ZnSnO having a thickness of about 10 nm_xComposed of ZnSn having 90 wt% Zn and 10 wt% SnAnd (4) depositing a gold target.

e) A second infrared reflective functional layer consisting of about 15 nanometers of silver from an almost pure silver target in a neutral argon atmosphere.

f) A layer of absorbing material consisting of about 1.8 nm palladium from a palladium target in the same neutral argon atmosphere as layer e).

g) The second sacrificial metal layer, which is composed of a 2.5 nm Ti layer, is oxidized by the plasma atmosphere used to deposit the next dielectric layer, in the same manner as the first sacrificial metal layer described above.

h) The third dielectric coating, the outer dielectric coating, consists of two oxide layers, which are deposited from cathodes of zinc-tin alloys with different compositions in a reactive atmosphere formed by a mixture of oxygen and argon. First zinc-tin mixed oxide ZnSnO having a thickness of about 7 nm_xDeposited from a metal target of a ZnSn alloy having 90 wt% Zn and 10 wt% Sn. A second zinc-tin mixed oxide having a thickness of about 15 nm was deposited from a ZnSn alloy target having 52 wt% Zn and 48 wt% Sn to form zinc stannate Zn₂SnO₄The spinel structure of (1).

It should be noted that the thickness of Ti is TiO₂The equivalent thicknesses (i.e. as a result of Ti oxidation) are given as they are in the finished product after the heat treatment. Furthermore, for layer g), Ti is already in its oxidized state in the intermediate glazing which is suitable for heat treatment.

TL ═ 19.7%; FS is 26.4% epsilon (emissivity) 0.030; the absorption rate was 67.4%, of which approximately 20% was attributable to the palladium layer of the absorbent material;

the transmitted hue is represented by the following value:

L*＝51.4；a*＝-6.1；b*＝-6.8

the reflected hue on the glass side is represented by the following value:

RL＝12.9％；L*＝42.7；a*＝-5.8；b*＝-31.9；λ_d480 nm; the purity was 49.9%.

The coated glass with the multilayer solar protection laminate formed on the glass sheets was then subjected to a hot tempering operation, during which it was exposed to a temperature of 690 ℃ for 6 minutes and subsequently quenched with a cold air jet. During this heat treatment, the titanium, still in metallic form (in particular in the first sacrificial metal layer c), is sufficiently oxidized to be transparent, while still forming an effective and stable barrier to protect the underlying silver layer. The upper protective layer of Ti is itself oxidized to TiO₂The transparent upper protective layer.

TL 59.1%; epsilon (emissivity) 0.026; rs 1.8 Ω/sq.; the absorption rate was 31.0%, of which approximately 20% was attributable to the palladium layer of the absorbent material;

the transmitted hue is represented by the following value:

l ═ 81.3; a ═ 3.0; b ═ 5.0; turbidity 0.12%;

the reflected hue on the glass side is represented by the following value:

RL＝9.9％；L*＝37.6；a*＝-0.1；b*＝-5.6；λ_D＝477nm；p＝9.6％。

it was found that the absorption value brought by the absorption layer does not decrease after the high temperature heat treatment.

TL is 53.0%; RL-12.7%; FS is 29.9%; 1.78 value of S1.1W/(m)²·K)；

The transmitted hue is represented by the following value:

L*＝77.9；a*＝-4.1；b*＝-4.0

the reflected hue is represented by the following value:

L*＝42.3；a*＝-0.9；b*＝-6.1；λ_D＝480nm；p＝15.6％。

visual inspection in the reflection of a double glazing shows a uniform tint and appearance across the surface. The present invention enables the formation of a double glazing having a very low solar coefficient, which maintains sufficient light transmittance and has a very high aesthetic appeal.

Examples 3 to 15

The following examples 3 to 15 were carried out in a similar manner to the above example 1 but with different structures, unless otherwise specified. The corresponding stack structures are given in table 1 below, using the abbreviations explained below:

d1 ═ a first dielectric coating, consisting of two or three oxide or nitride or optionally oxynitride layers. The nitride layer is deposited from a metal target in a reactive mixture of nitrogen and argon. This applies to the other dielectrics of the stack (if this is the case). Si used in these examples₃N₄The layer may be slightly oxidized in the form of SiOxNy. It should be noted that Si₃N₄And the ZnO layer may be doped with aluminium in a known manner.

D2 ═ an intermediate dielectric coating, if present in the examples, consisting of an oxide or nitride or optionally an oxynitride layer, like D1.

D3 ═ an outer dielectric coating, consisting of one or two oxide or nitride or optionally oxynitride layers, like D1.

IR1 and IR2 ═ first and second infrared-reflective functional layers.

P1 and P2 ═ first and second sacrificial metal layers, each consisting of one or two metal or metal alloy layers in metallic form or optionally in suboxidised form. These layers are intended to protect the infrared-reflective material (IR1 and IR2), such as silver, from oxidation in its place, particularly during the deposition of subsequent layers or during thermal treatment of the layer, if performed. In the final product, they are preferably almost completely oxidized.

Table 1 shows the state of these layers as they leave the sputtering apparatus prior to any thermal treatment, i.e., the sacrificial metal layer has been oxidized by the plasma used to deposit the subsequent layer (if so). In this case, they are present in their oxidized state rather than in the form in which they have been deposited. For example, TiO from column P1 and/or P2 of examples 3 to 7 and 11 to 15₂、ZAlO₅And Nb₂O₅Deposit in metallic form and oxidize during the subsequent oxide deposition and no longer constitute a reserve source of oxidation for any subsequent treatment. In contrast, NiCrOx and TiOx of examples 9, 10 and 13 were deposited in a low-oxidation form and remained low at the end of the deposition process, so they constitute a reserve source of oxidation for any subsequent treatment. NiCrOx (examples 9 and 13) was deposited from a cathode of NiCr in a slightly oxidizing reactive atmosphere using a controlled loop of oxidation states, while TiOx (example 10) was deposited from a ceramic TiOx cathode in an atmosphere consisting essentially of argon. Within the scope of the invention, TiOx may also be deposited in the same manner as NiCrOx. In example 15 (in P1), TiOx was also deposited from a ceramic TiOx cathode in an atmosphere consisting essentially of argon with a low oxygen fraction and in a strong oxidation state after subsequent oxide (ZSO5) deposition.

NiCr (P1, example 4) is a metal alloy with 80 wt% nickel and 20 wt% chromium used as a sacrificial metal. NiV (P1 and P2, example 6) is a metal alloy with 93 wt% nickel and 7 wt% vanadium also used as sacrificial metal. In these examples, (NiCr and NiV) both constitute sources of oxidation reserve for the subsequent high temperature heat treatment operation. They are oxidized after heat treatment.

In the case of TiRu15 of example 8, Ti constitutes the oxidation reserve for subsequent heat treatment operations, while Ru is the absorbing material that remains in absorbing metallic form after heat treatment.

CS — an upper protective layer, optionally consisting of two layers.

AB ═ absorbing layer if the absorbing material is deposited as a separate layer.

Otherwise, the absorbing material is present in the form of an alloy or doped with the infrared-reflecting material and/or with the sacrificial metal. In table 1, the absorbent material is shown in bold. The numbers shown next to the absorbing material represent the atomic percentage of the material in the alloy with the functional layer material or the sacrificial metal. For example, Ag: Pd3 indicates 3 atomic% of the absorbent palladium in silver, which applies equally to Ag: Pd2, Ag: Pd30, Ag: Co5, Ag: Os11 and Ag: Au 8. Furthermore, the TiRu15 showed 15 atomic% of the absorber ruthenium in the alloy with the sacrificial metal Ti.

Ag NiCr10 shows an alloy NiCr with 10 at% in silver (alloy with 80 wt% Ni and 20 wt% Cr). Such a functional layer containing the absorbing material may be deposited by co-sputtering from a silver cathode and a NiCr cathode or it may be obtained from a single cathode of an agnir alloy.

As a variant of example 12, use was made of Ag NiV10 with 10 atomic% NiV in silver (alloy with 93% Ni and 7% vanadium by weight) and the same results as listed above were obtained.

CoCr is an alloy with 80 wt% Co and 20 wt% Cr. This alloy can be deposited by magnetron without any problems related to the fact that CoCr is not ferromagnetic when deposited with pure Co and pure Ni in contrast, as in the case of NiCr or NiV mentioned above.

·ZSO₅Zinc-tin mixed oxide obtained by cathode sputtering in an oxidizing atmosphere from a metal target of ZnSn alloy having 52% Zn and 48% Sn;

·ZSO₉zinc-tin mixed oxide obtained by cathode sputtering in an oxidizing atmosphere from a metal target of ZnSn alloy having 90% Zn and 10% Sn;

·ZAlO₂and ZAlO₅Zinc oxide ZnO containing 2 or 5 atomic% of aluminum Al, respectively.

The glass plates of examples 3 to 15 had a thickness of 6 mm.

The glazings coated with the laminated structures according to examples 3 to 10 and 13 to 14 were subsequently subjected to a thermal tempering operation during which they were exposed to a temperature of 690 ℃ for 6 minutes and then quenched with a cold air jet.

The optical and energy-related properties of the coated glazings after tempering (if carried out) (examples 3 to 10 and 13 to 14) or after coating (if they have not been heat-treated (examples 11, 12 and 15)) are listed in table 2.

The values given for examples 3 to 8 and 13 to 14 are the values after heat treatment.

For examples 9 and 10, the values before heat treatment are also given in the row marked with italic AT (before tempering) (tables 2 and 3). It has been found that for both embodiments, the properties do not change significantly after the tempering treatment and therefore the tempered form and its similar untempered form can be put together.

In examples 3 to 10 and 13 to 14, it is noted that the coated glazing is absorbent and low in emissivity after tempering.

Examples 11, 12 and 15 are non-temperable laminated structures, i.e. they are used as such without heat treatment. The values given in table 2 for examples 11, 12 and 15 are therefore the values measured on leaving the layer deposition apparatus or after storage without heat treatment.

·L_RV*，a_RV*，b_RVIndicates the 1976 CIELAB value of the reflected hue on the glass side.

·λ_d(RV)And p_(RV)Indicating the dominant wavelength and purity of the reflected hue on the glass side.

Representing the change in hue during heat treatment.

TABLE 2

The light absorption amounts generated by the absorbing material in the different embodiments are about 4% in embodiment 3, about 30% in embodiment 4, about 11% in embodiment 5, about 10% in embodiment 6, about 32% in embodiment 7, about 18% in embodiment 8, about 28% in embodiment 9, about 22% in embodiment 10, about 4% in embodiment 11, about 9% in embodiment 12, about 21% in embodiment 13, about 20% in embodiment 14, and about 17% in embodiment 15, respectively. This light absorption value caused by the absorbing material in the laminated structure is not affected by the high-temperature heat treatment applied to the laminated structures of examples 3 to 10 and 13 to 14.

As a variant of example 12, the absorber material NiCr present as an alloy in silver of the second functional layer at 10 atom% NiCr was replaced by 10 atom% Ti in silver or by 4 atom% Pd in silver, without changing the thickness of the functional layer (IR2), and the same optical properties, including the hue, were obtained as given in table 2 for example 12. Example 12 and its variants relate to a non-temperable laminate structure. When referring to a temperable laminate structure, the alternative absorbent material must be selected from the absorbent materials listed above as being preferred for forming a temperable laminate structure, namely the following materials: pd, Pt, Au, Ir, Rh, Ru, Os, Co, La, Ce, Pr, Nd, and alloys thereof.

The optical and energy-related properties of the coated glazing assembled in the same manner as in example 1 with 6 mm transparent glass sheets into a double glazing and having a 15 mm gap filled with 100% argon are listed in table 3. The glazing is viewed from the laminated structure at position 2 on the outer sheet in a double glazing, i.e. from the glass side, the glazing with the laminated structure is viewed first, and then the transparent glass sheet without the layers is viewed. The assembled double glazing units with toughened laminate structures of examples 9 and 10 can be placed aesthetically with their similar assemblies with the same non-toughened laminate structure, since Δ E is very low.

TABLE 3

Claims

1. Multilayer solar protection laminate structure formed on a sheet of vitreous material, comprising at least one functional layer comprising a silver-based material reflecting infrared radiation and at least two dielectric coatings, one of which is a first dielectric coating deposited directly on the sheet of vitreous material, the other coating being located externally with respect to the functional layer or layers, each functional layer being surrounded by a dielectric coating, wherein said laminate structure has a solar coefficient FS of less than 45% and a light transmission TL of less than 70% when deposited on a sheet of ordinary transparent soda-lime float glass 6 mm thick, characterized in that it comprises a substantially metallic absorbing material placed next to the functional layer or contained within such a functional layer, the material being based on at least one of the following elements: pd, Pt, Au, Ir, Rh, Ru, Os, Co, Ni, Cu, Cr, La, Ce, Pr, Nd, W, Si, Zn, Mo, Mn, Ti, V, Nb, Hf, Ta and alloys thereof,

wherein the outer dielectric coating of the laminated structure comprises at least one zinc-tin mixed oxide based layer containing at least 20% tin and/or an oxygen diffusion barrier layer having a thickness greater than 5 nm selected from the group consisting of: AlN, AlNxOy, Si₃N₄、SiOxNy、SiO₂ZrN, SiC, SiOxCy, TaC, TiN, TiNxOy, TiC, CrC, DLC, and alloys thereof, and nitrides or oxynitrides of the alloys.

2. The laminated structure according to claim 1, characterized in that the nitride or oxynitride of the alloy is selected from the group consisting of SiAlOxNy or SiTixNy.

3. The laminate structure according to one of claims 1 to 2, characterized in that the absorbent material is contained in a functional layer.

4. A laminated structure according to claim 3, characterized in that the functional layer contains 1 to 30 atomic% of an absorbing material which is an alloy with or doped with a silver-based material which reflects infrared radiation.

5. The laminate structure of claim 4 wherein the functional layer comprises 5 to 20 atomic percent of the absorbent material.

6. The laminate structure of claim 4 wherein the functional layer comprises 5 to 10% of the absorbent material.

7. The laminate structure according to one of claims 4 to 6, characterized in that the absorbent material contained in the functional layer is selected from the following materials: ni, Cr, NiCr, CoCr, W, Si and NiV.

8. The laminate structure according to one of claims 4 to 6, characterized in that the absorbent material contained in the functional layer is selected from the following materials: os, Co, Pd, Pt, Ir, Ru and Rh.

9. The laminate structure according to one of claims 1 to 2, characterized in that the absorption material at least partially forms part of a separate layer deposited below or above and in direct contact with the functional layer.

10. The laminate structure of claim 9 wherein the absorber material is alloyed with a sacrificial metal for protecting the functional layers.

11. The laminate structure according to claim 9, characterized in that the absorbing material constitutes the main part of said separate layer deposited below or above and in direct contact with the functional layer.

12. The laminated structure according to claim 11, characterized in that the separate layer of absorbing material has a physical thickness of 0.3 to 10 nm.

13. The laminate structure of claim 12 wherein the discrete layer of absorbent material has a physical thickness of from 0.4 to 5 nanometers.

14. The laminated structure according to one of claims 12 to 13, characterized in that the separate layer of absorbing material has a physical thickness of 0.8 to 3 nm.

15. The laminate structure according to one of claims 1 to 2, characterized in that the absorbing material is selected from at least one of the following elements: pt, Pd, Co, Ir, Ru, Rh, Os, CoCr, Ti, and NiCr and alloys thereof.

16. The laminate structure of claim 15 wherein the absorbent material is palladium.

17. The laminate structure according to one of claims 1 to 2, characterized in that 4 to 35% of the light absorption of the laminate structure is attributable to the absorbing material.

18. The laminate structure of claim 17 wherein 8 to 22% of the light absorption of the laminate structure is attributable to the absorbing material.

19. The laminated structure according to one of claims 1 to 2, characterized in that the first dielectric coating and the outer dielectric coating comprise at least one zinc-tin mixed oxide based layer containing at least 20% tin.

20. The laminate structure according to any one of claims 11 to 13, characterized in that the laminate structure comprises, in order from the sheet of vitreous material, at least the following layers:

a) a first dielectric coating layer is formed on the substrate,

b) a silver-based functional layer,

c) an absorption layer is arranged on the outer surface of the substrate,

e) an outer dielectric layer.

21. The laminated structure according to one of claims 1 to 2, characterized in that the laminated structure comprises at least two functional layers separated by at least one intermediate dielectric coating.

22. The laminate structure of claim 21 wherein the absorbent material is disposed adjacent to or contained in the functional layer furthest from the sheet of vitreous material and the hue does not change significantly when the absorbent material is exchanged for another absorbent material providing the same level of absorption.

23. The laminate structure according to claim 21, characterized in that the laminate structure comprises, in order from the sheet of vitreous material, at least the following layers:

a) a first dielectric coating layer is formed on the substrate,

d) an intermediate dielectric coating layer is formed on the substrate,

e) a second silver-based functional layer,

f) an absorption layer is arranged on the outer surface of the substrate,

h) an outer dielectric layer.

24. The laminate structure according to claim 21, characterized in that the laminate structure comprises, in order from the sheet of vitreous material, at least the following layers:

d) an intermediate dielectric coating layer is formed on the substrate,

e) a second silver-based functional layer,

f) a palladium-based absorption layer,

25. The laminate structure of claim 24 wherein all of the dielectric coatings comprise a zinc-tin mixed oxide base layer comprising 50% tin and zinc, and a zinc-tin mixed oxide base layer comprising no more than 10% tin and at least 90% zinc, the latter layer each time being disposed closer to the subsequent functional layer than the 50% tin mixed oxide layer.

26. The laminate structure according to one of claims 1 to 2, characterized in that the laminate structure ends with a thin carbon-based protective layer having a thickness of 1.5 to 10 nm.

27. Glass sheet material with a laminated structure according to one of claims 1 to 26.

28. Glass sheet according to claim 27, characterized in that the glass sheet has a hue measured on glass side reflection represented by L, -4 to +3, and b-4 to-16 of from 30 to 55.

29. Glass sheet according to claim 28, characterized in that L is 40 to 50.

30. Glass sheet according to claim 28, characterized in that a is-2.5 to + 1.5.

31. Glass sheet according to claim 28, characterized in that b is from-6 to-13.

32. Glass sheet according to one of claims 27 to 31, characterised in that the glass sheet is subjected to a tempering and/or bending heat treatment after the deposition of the multilayer laminated structure.

33. Glass sheet according to claim 32, characterized in that 4 to 35% of the light absorption of the laminated structure after heat treatment is attributable to the absorbing material.

34. Glass sheet according to claim 33, characterized in that 8 to 22% of the light absorption of the laminated structure after heat treatment is attributable to the absorbing material.

35. Assembly formed by a first group comprising at least one glass sheet according to one of claims 32 to 34 and a second group comprising at least one glass sheet according to one of claims 27 to 31 which has not been heat-treated, characterized in that the two groups have a similar visual appearance of reflection on the glass side, so that they can be juxtaposed without significant visual differences.

36. A multiple glazing comprising a glass sheet according to any of claims 27 to 34.

37. Multiple glazing according to claim 36 characterised in that it has a solar factor FS of 15 to 40%, a light transmission of at least 30% and a relatively neutral transmission colour and a neutral to bluish reflection colour on the side of the glass sheet with the laminated structure.

38. Multiple glazing according to claim 37, characterised in that it has a solar coefficient FS of 20 to 35% and a light transmission of at least 45%.

39. Multiple glazing according to claim 38, characterised in that the solar coefficient FS is between 25 and 35%.

40. Multiple layer glazing according to claim 38 characterised in that the light transmission is at least 50%.

41. Laminated glazing according to claim 38, characterised in that the light transmission is at least 55%.

42. A multiple glazing according to one of the claims 36 to 41 characterised in that the multiple glazing has a reflected tint on the side of the glass sheet bearing the laminated structure, represented by L from 40 to 55, a from 1.5 to-6, and b from-3 to-15, wherein the laminated structure is placed towards the inner space of the multiple glazing.

43. A multiple glazing according to claim 42 characterised in that L is from 45 to 52.

44. A multiple layer glazing according to claim 42 characterised in that a is from 0.5 to-4.

45. A multiple layer glazing according to claim 42 characterised in that b is from-5 to-12.