Material and glazing comprising said material

The invention relates to the field of materials containing a glass base coated with a photocatalytic layer.

It is known that photocatalytic layers, in particular, based on titanium oxide, make the substrates that they cover, self-cleaning and non-dirty. These characteristics are based on two properties. First, titanium oxide has photocatalytic properties, that is, with suitable radiation, usually ultraviolet radiation, it is capable of catalyzing the decomposition of organic compounds. This photocatalytic activity is initiated inside the layer as a result of the formation of an electron-hole pair. In addition, titanium oxide has a very pronounced hydrophilicity when it is irradiated with this type of radiation. This high hydrophilicity removes mineral contaminants when flushed with water, such as rainwater. Such materials, in particular glazing, are described, for example, in application EP-A-0850204.

There are glasses that combine this ability to self-clean and not get dirty with sunscreen properties. Sun protection is understood as the ability to reduce the amount of solar energy that can pass through glass and heat living spaces and cabs of vehicles. Window panes endowed with such properties make it possible to avoid excessive heating of the aforementioned rooms or cabins and, if necessary, limit the energy consumption associated with their conditioning. So, from the application UO 03/050056 it is known about the application of photocatalytic coatings on colored glass. However, colored glass has a low selectivity, which corresponds to the ratio of light transmission to energy transmission. There are also glazings, usually called a two-layer coating, which contain a photocatalytic layer on one side and a sun-protection coating on the other side. The advantage of this arrangement is that the sun-protection coating, which often has low durability under climatic conditions, is protected while on side 2 of the window, that is, inside the building, while the photocatalytic coating is on side 1, that is, outside the building, where most of all good. However, such window panes create processing difficulties, since there is a danger that the layer or laying of the layers deposited on the inside may be damaged during conveyor delivery, in particular due to contact with conveyor rollers. Therefore, it would be useful to be able to offer window panes having on the same side, that is, on side 1, sun protection functions and self-cleaning functions. However, attempts to solve this problem to date have been futile due to the poor durability of the resulting layings under climatic conditions.

The first objective of the invention is to provide photocatalytic materials that can be introduced into sun glazing, which would not have the above-mentioned disadvantages. A second object of the invention is to provide sun-protection glazing having good durability under climatic conditions according to standard ΕΝ 1096-2: 2001. A third object of the invention is to provide materials having a neutral color in transmittance and / or reflection.

These goals are achieved by a material containing a glass base coated on at least one of its sides by laying thin layers containing, in the direction from said base, at least one lower dielectric layer, at least one functional layer of metal or metal nitride, at least one upper dielectric layer, at least one layer of titanium oxide, at least partially crystallized in the form of anatase, wherein said metal or metal nitride is based on N6. Ν6Ν, Y, ^ Ν, Ta, ΤαΝ or any of their alloys or solid solutions.

The selected metals or nitrides, in combination with dielectric layers and a layer of titanium oxide, unexpectedly provide excellent durability under climatic conditions and satisfy the requirements of standard ΕΝ 1096-2: 2001 even after 56 days of testing. Therefore, such glazing can be placed so that the laying of the layers is on side 1, that is, outside the building, where the photocatalytic layer can fully fulfill its role in relation to dirt and atmospheric pollution. Thus, this combination allows us to offer glazings that have the ability to self-clean and not get dirty at the same time and have sunscreen properties, but which do not have the disadvantages of double coatings known from the prior art.

Preferably, the base is a glass sheet. The sheet may be flat or curved and may have any size, in particular more than 1 m. The glass is preferably sodium-calcium-silicate glass, but other types of glass, such as borosilicate or aluminosilicate glasses, can also be used. The glass may be transparent or extra-transparent, or be colored, for example, blue, green, amber, bronze or gray. The thickness of the glass sheet is usually from 0.5 to 19 mm, in particular from 2 to 12 mm, even from 4 to 8 mm.

Laying thin layers preferably does not contain layers of silver or copper, since these layers can give the glass poor weather resistance, which is especially harmful when laying the layers should be on side 1 of the window glass.

The best results, in particular with regard to durability under climatic conditions, are obtained when the metal or metal nitride is selected from Ν6Ν, N6, Y ^ U. These metals or nitrides also have good absorption characteristics in the visible and infrared regions

- 1,020,943 spectra. The thickness of the metal layer or metal nitride should be selected depending on the desired light transmission. Usually it varies from 3 to 50 nm, in particular from 5 to 30 nm, even from 5 to 20 nm. The light transmission of the material is preferably from 5 to 70%, in particular from 10 to 60%.

A single or each lower dielectric layer is designed to protect a metal or nitride layer from the diffusion of alkaline ions from the base, from oxidation and from delamination. Preferably, one or two upper dielectric layers are used. A single or each upper dielectric layer is designed to reduce internal reflection from a metal or nitride layer and to protect this layer from corrosion and mechanical damage (scratches, abrasion, etc.). This at least one lower dielectric layer and / or at least one upper dielectric layer is preferably selected from silicon, aluminum, nitride or oxy nitride oxide, tin oxide or mixed tin and zinc oxide. Silicon nitride is preferred since it provides excellent mechanical strength and hardening resistance and can be easily applied by cathodic sputtering in the magnetron mode. Each of these layers can be pure or alloyed. Thus, silicon oxide or silicon nitride layers are often doped with an atom such as aluminum to facilitate their deposition by cathodic sputtering. The thickness of the single or each lower dielectric layer and / or the single or each upper dielectric layer is preferably from 5 to 100 nm, in particular from 10 to 50 nm.

When the functional layer is metallic, in particular of niobium or niobium-based, it is preferable to introduce a blocking layer between the functional layer and the upper dielectric layer closest to the functional layer, and even between the functional layer and the lower dielectric layer closest to the functional layer. This blocking layer is designed to prevent oxidation or nitriding of the functional metal layer during possible heat treatments, for example, quenching. This blocking layer is very thin, preferably from 1 to 5 nm in thickness. It preferably consists of a metal selected from titanium or chromium, or from an alloy of nickel and chromium. When the functional layer is metallic, the presence of a blocking layer or layers makes the stacking of the layers capable of hardening, in the sense that the laying of the layers has similar optical properties before and after hardening.

On the functional layer, in particular when it consists of nitride, an additional layer of nitride can be applied, for example, from niobium, titanium, zirconium or chromium nitride. This additional layer makes it possible to select reflection characteristics, in particular colorimetric parameters, if necessary.

Preferably, at least one layer of silicon oxide is located between at least one upper dielectric layer and at least one layer of titanium oxide, at least partially crystallized in the form of anatase, and / or between the base and the lower dielectric layer closest to the base. This additional layer improves the photocatalytic activity of the coating. In a second alternative, changes in the color of the stacking layers in the reflection associated with possible fluctuations in the thickness of the silicon oxide layer are minimized. On the other hand, in the first alternative, the thickness and uniformity of the silicon oxide layer should be ideally adjusted in order to control the color of the layers in reflection. The single or each layer of silicon oxide preferably has a thickness of from 5 to 100 nm, in particular from 10 to 40 nm. The silicon oxide layer may be pure or doped, for example, with aluminum atoms.

The preferred layings are as follows:

- ετθΚΛθ / 5ί₃Ν₄/ ΝΒΝ / δΐ₃Ν₄/ Τί0₂

- 0τεκηο / 5ί₃Ν4 / ΝΒΝ / 3ί₃Ν4 / 3ΐ02 / Τί0₂

- Glass / 5t0₂/51₃S₄/ S / 51₃N4 / T ± 0₂

- 0τβκηο / 3ί0₂/ δϊ₃Ν4 / ΝΒΝ / 8ΐ₃Ν4 / 3ί0₂/ Τί0₂

- Οτθκπο / 5ί₂Ν4 / ΝΝ / 3ί₃Ν4 / Τΐθ2

- 0τθκηο / 3ί₃Ν4 / ΜΝ / 3ί₃Ν₄/ 3ί0₂/ ΤίΟ₂

- 0τθκπο / 3ϊ0₂/ 8ί₃Ν4 / ΜΝ / 3ί₃Ν4 / Τί0₂

- 0τθκηο / 3ί0₂/ 3ΐ₃Ν4 / ΗΝ / 3ί₃Ν₄/ 3ί0₂/ ΤίΟ₂

- Stekpo / 31₃S4 / T1 / S1 / T1 / 31zK₄/ T10₂

- 0τθκηο / 3ί₃Ν4 / Τϊ / ΝΒ / Τί / 3ί₃Ν4 / 3ί0₂/ Τΐ0₂

- 0τβκηο / 3ϊ0₂/ 3ΐ₃Ν4 / Τϊ / ΝΒ / Τί / 8ί₃Ν₄/ ΤίΟ₂

- 0τθκΠθ / 3ί02 / 3ί₃Ν4 / Τΐ / No. / Τί / 3ί₃Ν4 / 5ίΟ₂/ ΤίΟ₂

In these non-limiting examples of stackings according to the invention, the blocking layer of titanium can be replaced by a layer of chromium. The thickness ranges for the various laying layers are described previously and will not be called again here so as not to complicate the text.

- 2 020943

Titanium oxide can be pure or alloyed, for example, transition metals (for example, A, Mo, V, N6). lanthanide ions or noble metals (such as platinum, palladium), or nitrogen or carbon atoms. These different forms of doping can either increase the photocatalytic activity of the material, or shift the band gap of titanium oxide to wavelengths close to or lying in the visible spectrum region.

The titanium oxide layer is usually the last layer in the stacking of the layers deposited on the substrate, in other words, the stacking layer farthest from the substrate. Indeed, it is important that the photocatalytic layer is in contact with the atmosphere and its pollutants. However, it is permissible to deposit a very thin layer on the photocatalytic layer, usually non-continuous or porous. This can be, for example, a layer based on a noble metal, designed to enhance the photocatalytic activity of the material. We can also talk about thin hydrophilic layers, for example, of silicon oxide, as taught by the application of AO 2005/040058 or AO 2007/045805.

The thickness of the titanium oxide layer is preferably from 5 to 50 nm, in particular from 5 to 20 nm.

The use of laying layers on just one side of the base can significantly simplify the deposition process, reduce its cost and avoid the risk of damage to the layers during their transportation or handling.

The material according to the invention preferably has an energy transmission (in accordance with the standard ΝΡ ΕΝ 410: 1998) from 2 to 70%, in particular from 5 to 65%.

The invention also relates to a method for producing a material in which stacking layers are deposited by cathodic sputtering in the magnetron mode or by chemical vapor deposition (Ονϋ).

In the process of cathodic sputtering, in particular with support by a magnetic field (magnetron method), the components excited by the plasma knock out atoms from the target located opposite the base to be coated. For the deposition of a layer of titanium oxide, the target may consist, in particular, of metallic titanium or of ΤίΟ_χ, and the plasma must contain oxygen (then we speak of reactive cathodic sputtering). It is also possible to precipitate δί layers₃Ν₄ or δίΟ₂ using a silicon target doped with aluminum in a plasma containing argon and, accordingly, nitrogen or oxygen. A functional layer of metal or nitride can be deposited using a metal target, respectively, in an inert atmosphere (e.g. argon) or in a chemically active atmosphere containing nitrogen.

Chemical vapor deposition, usually denoted by its English acronym ΟνΌ, is a pyrolysis method based on gaseous precursors that decompose under the influence of the heat of the base. In the case of titanium oxide, the precursors may be, for example, titanium tetrachloride, titanium tetraisopropoxide or titanium tetraorthobutoxide.

The deposition is preferably followed by heat treatment, in particular quenching, bending, annealing or rapid processing using laser radiation or flame, in particular when a layer of titanium oxide has been deposited by cathodic sputtering. This heat treatment is intended to crystallize titanium oxide in the form of anatase. Quick processing is preferably the processing as described in the application AO 2008/096089.

The object of the invention is also glazing containing at least one material according to the invention. Glazing can be simple or multi-layer (in particular, of two or three layers), in the sense that it can contain several sheets of glass separated by a space filled with gas. Glazing may also be glued and / or hardened and / or hardened and / or bent. In the case of simple or multi-layer glazing, a sunscreen is preferably applied to side 1.

The sun glazing thus obtained has, in addition, the ability to self-clean, not to get dirty, not to fog and improve visibility during rain. When the functional layer is a metal, for example, N6, the emissivity of the stacking layers is reduced, usually to values ​​of 0.5 or less, even 0.3. Thus, the styling has both sun protection properties and a low emissivity. When laying the layers is applied to side 1, this latter property is particularly advantageous in order to limit condensation (fogging and / or frost) on the surface of the double-glazed windows, in particular when they are inclined (for example, when they are built into the roof or verandas). The presence of a low-emitting layer on side 1 allows you to limit heat transfer with the external environment at night and, therefore, to keep the surface temperature of the glass above the dew point. Thus, the appearance of effusion or frost is greatly attenuated or even completely prevented.

In the case of simple glazing, the laying of layers can also be placed on side 2, which ensures ease of cleaning and the ability not to fog.

The other side of the base coated according to the invention, or, if necessary, one side of the other base in the case of a double-glazed unit, can be covered with another functional layer or by laying functional layers. This may be, in particular, another photocatalytic layer, for example, another laying of layers according to the invention. It can also be layers or laying layers with thermal

- 3 020943 function, in particular, heat-shielding or with low emissivity, for example, systems containing a silver layer protected by dielectric layers. It can also be a mirror layer, in particular, based on silver. Finally, it can be varnish or enamel, the purpose of which is to make the glazing opaque in order to form a decorative facade panel designed for a window sill. The sill wall is located on the facade next to transparent window panes and allows you to get completely glass facades, homogeneous in terms of aesthetic appearance.

Finally, an object of the invention is the use of glazing according to the invention as a sun glazing for buildings or vehicles (land, air, rail). The glazing according to the invention is preferably used on side 1, in the sense that the laying of the layers is outside the building or vehicle. For applications in the field of buildings, glazing is preferably used on verandas, facades or in the roof. For automotive applications, glazing can profitably form a roof.

The invention will become more apparent in light of the following non-limiting examples.

All examples, comparative or according to the invention, are implemented by the method of cathodic sputtering in the magnetron mode on transparent glass substrates sold by the applicant company under the trademark P1ash1ih.

Layers of silicon nitride are obtained based on a silicon target doped with 8 wt.% Aluminum in an atmosphere consisting of 45% argon and 55% nitrogen. Layers of niobium are obtained on the basis of a target from niobium in an argon atmosphere. Layers of niobium nitride were obtained using a target of the same type, but in an atmosphere consisting of 45% argon and 55% nitrogen. Layers of titanium are obtained using a titanium target in an argon atmosphere. As for the layers of titanium oxide, they are obtained on the basis of a titanium target in an atmosphere consisting of argon and oxygen, or on the basis of a target of substoichiometric titanium oxide in an argon atmosphere enriched with 1% oxygen. Silica layers were obtained using a silicon target doped with 8 wt.% Aluminum in an atmosphere consisting of 75% argon and 25% oxygen.

1st series of examples.

Tab. 1 shows the composition and thickness for comparative example C1 and for examples according to the invention 1-5. Layering of layers is carried out in the order indicated in the table, with the first line corresponding to the layer farthest from the base, and the last line corresponding to the layer in contact with the base. As in the rest of the description, the thicknesses are physical thicknesses, expressed in nm.

Table 1

<td></td><td>C1</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>

<td>ΤίΟ₂</td><td> 0</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td><td> 10</td>

<td>Xxo₂</td><td> 0</td><td> 0</td><td> 0</td><td> 23</td><td> 20</td><td> 10</td>

<td>5ί 3Ν4</td><td> 31</td><td> 31,1</td><td> 18</td><td> 18</td><td> 0</td><td> 5</td>

<td>mm</td><td> 6,6</td><td> 6,6</td><td> 6,8</td><td> 6,8</td><td> 7,0</td><td> 7,0</td>

<td>513Ν4</td><td> 11,3</td><td> 11,3</td><td> 12</td><td> 12</td><td> 20</td><td> 20</td>

In the table. 2 below shows the optical properties for comparative example C1 and examples according to the invention 1-5.

Indicated:

light transmission (TB) and light reflection from the side of the glass (KEu) and from the side of the layers (KB_FROM), as well as energy transmittance (TE) according to the standard ΝΡ ΕΝ 410: 1998, the corresponding color parameters are b * a * b * (in transmission and reflection from the glass side and from the layer side), calculated under the conditions of illuminator Ό65 and standard observer C1E -1931.

- 4 020943

table 2

Ή Γϊ Гг Гз Г5 Γϊ

<td>I. &lt;%)</td><td> 50,2</td><td> 54,2</td><td> 51,7</td><td> 57,2</td><td> 55,2</td><td> 51,1</td>

<td>b *</td><td> 76,2</td><td> 78, 6</td><td> 77,1</td><td> 80,3</td><td> 79,2</td><td> 76,7</td>

<td>but*</td><td> -1,5</td><td> -1,4</td><td> -1,3</td><td> -1,6</td><td> -1,2</td><td> -1,3</td>

<td>B *</td><td> -1,8</td><td> -2, 1</td><td> -1,6</td><td> -3,3</td><td> -2,0</td><td> -2,7</td>

<td>B_FROM (%)</td><td> 16,7</td><td> 14,0</td><td> 17,3</td><td> 8,9</td><td> 15,4</td><td> 17,4</td>

<td>b-</td><td> 47, 8</td><td> 44, 3</td><td> 48, 6</td><td> 35,8</td><td> 46,2</td><td> 48,8</td>

<td>but*</td><td> 0,6</td><td> 0,6</td><td> 0,6</td><td> 1,5</td><td> -0,7</td><td> 0, 1</td>

<td>B *</td><td> 0,7</td><td> 1,9</td><td> -0, 3</td><td> 11,8</td><td> 4,0</td><td> 2, 1</td>

<td> &lt;%)</td><td> 17,0</td><td> 25,3</td><td> 19, 9</td><td> 20, 8</td><td> 16,8</td><td> 15,8</td>

<td>b *</td><td> 48,2</td><td> 57,3</td><td> 51,7</td><td> 52, 8</td><td> 48,0</td><td> 46, 6</td>

<td>but*</td><td>-ι, 1</td><td> -2, 8</td><td> 1,2</td><td> -3, 1</td><td> -1,9</td><td> -1,0</td>

<td>B *</td><td> -9,8</td><td> -8, 1</td><td> -11,1</td><td> -3,2</td><td> -8,0</td><td> -9,5</td>

<td>TE (¾)</td><td> 45,3</td><td> 49, 0</td><td> 47, 6</td><td colspan="2"> 50,9 | 50,2</td><td> 46,0</td>

Samples from Examples C1 and 1-5 were then annealed at a temperature of 620 ° C for 10 minutes. Tab. 3 below shows the optical properties for comparative example C1 and examples according to the invention 1-5 after annealing. It also results in color changes in transmission and reflection caused by annealing. These changes are expressed by ΔΕ * (which corresponds to the square root of the sum of the squares of the differences of the color parameters before and after annealing). The indices ΐ, ν or c relate respectively to transmission, reflection from the glass side and reflection from the layer side.

Table 3

<td></td><td>C1</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>

<td>TH (%)</td><td> 51,6</td><td> 54</td><td> 51,4</td><td> 56, 6</td><td> 56, 9</td><td> 50,4</td>

<td>b *</td><td> 77, 0</td><td> 78,4</td><td> 76, 9</td><td> 79, 9</td><td> 80,1</td><td> 76,3</td>

<td>but*</td><td> -1,6</td><td> -1, 9</td><td> -1,8</td><td> -2,0</td><td> -1, 4</td><td> -1,5</td>

<td>b *</td><td> -2,4</td><td> -2, 8</td><td> -2, 9</td><td> -3, 9</td><td> -2,9</td><td> ~3,5</td>

<td>P-b, &lt;%)</td><td> 15,6</td><td> 11,9</td><td> 15, 3</td><td> 6,8</td><td> 14,5</td><td> 16, 4</td>

<td>b *</td><td> 46,5</td><td> 41,1</td><td> 46,0</td><td> 31,3</td><td> 44,9</td><td> 47,5</td>

<td>but*</td><td> 1, 2</td><td> 2,0</td><td> 1,7</td><td> 3,8</td><td> 0, 3</td><td> 0,8</td>

<td>b *</td><td> 0,4</td><td> 0, 0</td><td>0, ι</td><td> 8,8</td><td> 3,7</td><td> 2, 9</td>

<td>R. b, · &lt;%&gt;</td><td> 15, 4</td><td> 24, 7</td><td> 19,2</td><td> 20,6</td><td> 16,5</td><td> 15,4</td>

<td>b *</td><td> 4 6,2</td><td> 56, 8</td><td> 50,9</td><td> 52, 5</td><td> 47, 6</td><td> 46,2</td>

<td>but*</td><td> 0,7</td><td> -2,8</td><td> -0,9</td><td> -3, 1</td><td> -1,4</td><td> -0,6</td>

<td>B *</td><td> -9,6</td><td> -3,1</td><td> -11,5</td><td> -3,1</td><td> -8,2</td><td> -10,1</td>

<td>TE (%)</td><td> 46, 2</td><td> 47, 6</td><td> 45,9</td><td> 49,1</td><td> 51,8</td><td> 44, 8</td>

<td>ΔΕ *_ε</td><td> 1,0</td><td> 0, 9</td><td> 1,4</td><td> 0,9</td><td> 1,3</td><td> 0, 9</td>

<td>ΔΕ * ₌</td><td> 1,5</td><td> 3,9</td><td> 2, 9</td><td> 5,8</td><td> 1,7</td><td> 1,6</td>

<td>ΔΕ * „</td><td> 2,8</td><td> 0, 5</td><td> 0,9</td><td> 0,2</td><td>Oh 6</td><td> 0,8</td>

Low values ​​of ΔΕ * show that the colorimetric properties of the layings of the layers did not change significantly as a result of annealing.

The photocatalytic activity of comparative sample C1 and samples according to the invention 1-5 was measured according to the following test.

An aqueous solution of methylene blue is brought into contact in an impermeable chamber with a coated base (the latter forming the bottom of the chamber). After exposure to ultraviolet radiation for 30 minutes, the concentration of methylene blue is measured by measuring light transmission. The value of photocatalytic activity, expressed in g / (l-min), corresponds to a decrease in the concentration of methylene blue per unit exposure time.

Tab. 4 reproduces the results.

- 5 020943

Table 4

<img file="EA020943B1_D0001.tif" />

Thus, the presence of a silicon oxide layer between the second dielectric layer and the photocatalytic layer can significantly increase the photocatalytic activity of the coating. Analysis by secondary ion mass spectroscopy (8-8) confirms that the amount of sodium inside the photocatalytic layer is less when there is a layer of silicon oxide.

2nd series of examples.

Tab. 5 shows the composition and thickness for comparative example C2 and for examples according to the invention 6 and 7. Layering of the layers is carried out in the order shown in the table, the first line corresponding to the layer farthest from the substrate, and the last row corresponding to the layer in contact with the substrate . As in the rest of the description, the thicknesses are physical thicknesses expressed in nm.

Table 5

<img file="EA020943B1_D0002.tif" />

Samples C2 and 6 and 7 were quenched. The optical properties of the samples after quenching are given in table. 6.

Table 6

<td></td><td>C2</td><td> 6</td><td> 7</td>

<td>TH (%)</td><td> 51,4</td><td> 52,5</td><td> 51,5</td>

<td>b *</td><td> 76, 9</td><td> 77,6</td><td> 77,0</td>

<td>but*</td><td> -1,5</td><td> -1,8</td><td>ι ⁰⁰</td>

<td>b *</td><td> 0,2</td><td> -2,0</td><td> -1,9</td>

<td>kj_from (¾)</td><td> 16, 9</td><td> 14,4</td><td> 15, 4</td>

<td>b *</td><td> 48, 1</td><td> 44,8</td><td> 46,2</td>

<td>but*</td><td> 0,4</td><td> 0, 6</td><td> 0,7</td>

<td>b *</td><td> 0,9</td><td> 4,0</td><td> 2,7</td>

<td>КЪ „{%)</td><td> 18, 5</td><td> 17,6</td><td> 15,4</td>

<td>but*</td><td> -1,1</td><td> -2,0</td><td> -1,4</td>

<td>B *</td><td> -9,6</td><td> -11,1</td><td> -11, 6</td>

Hardened samples C2, 6 and 7 were subjected to various tests for durability under climatic conditions, described in standard ΕΝ 1096-2: 2001.

We are talking about tests for resistance to condensation according to Appendix B of standard ΕΝ 1096-2: 2001, designated by HH, against acid corrosion, according to Appendix C of the above standard, indicated by 8O₂, for resistance to neutral salt fog, according to Appendix Ό of the aforementioned standard, designated Β8Ν.

Tab. 7 shows the results in terms of visual inspection, color change

- 6,020,943 and reflection and light transmission characteristics after 56 days of testing. The lines of visual con

<img file="EA020943B1_D0003.tif" />

The quenched samples C2, 6 and 7 were also subjected to accelerated aging testing, consisting in immersion in boiling demineralized water for 2 hours. Changes in colorimetric parameters due to this treatment are presented in Table. 8.

Table 8

<img file="EA020943B1_D0004.tif" />

Laying layers according to the invention have generally better resistance to climatic conditions than the comparative system, in particular in the accelerated aging test in boiling water, as well as in tests for resistance to condensation and neutral salt fog. Thus, the titanium oxide layer, in addition to providing photocatalytic properties, significantly improves the durability of the glazings according to the invention under climatic conditions, which allows placing layers on the side 1.

For comparison, sun protection layers containing a silver layer between several layers of silicon nitride and coated with a layer of titanium oxide did not pass the tests of ΒδΝ, HH and §O₂ even after 21 days of testing.

3rd series of examples.

Table 9 shows the composition and thickness for comparative example C3 and for the example according to the invention 8. The layers are laid in the order shown in the table, the first line corresponding to the layer farthest from the substrate and the last row corresponding to the layer in contact with the substrate. As in the rest of the description, the thicknesses are physical thicknesses, expressed in nm.

- 7 020943

Table 9

<td></td><td>Sz</td><td> 8</td>

<td>ΤίΟ₂</td><td> 0</td><td>B</td>

<td>Ξί₃Ν₄</td><td> 45</td><td> 38</td>

<td>Τί</td><td> 1</td><td> 1</td>

<td>Q</td><td> 19</td><td> 19</td>

<td>τί</td><td> 1</td><td> 1</td>

<td>3ί₃Ν₄</td><td> 40</td><td> 40</td>

In the table. 10 summarizes the colorimetric and energy characteristics for examples C3 and 8 after quenching. The term TE corresponds to energy transmission according to the standard ΝΕ ΕΝ 410: 1998.

Table 10

<img file="EA020943B1_D0005.tif" />

standing immersed in boiling demineralized water for 2 hours. Changes in colorimetric parameters due to such processing are presented in table. eleven.

As above in the text, these changes are expressed by the quantity ΔΕ * (which corresponds to the square root of the sum of the squares of the differences of the color parameters b * a * b * before and after annealing). The indices ΐ, ν or c relate respectively to transmission, reflection from the glass side and reflection from the layer side.

Table 11

<img file="EA020943B1_D0006.tif" />

The comparative sample shows a very strong deterioration in appearance, in particular, in reflection from the side of the layer, while the optical properties of the sample according to the invention have not changed.

The samples were also subjected to the Β8Ν test (resistance to neutral salt fog), described in Appendix 820943 of standard ΕΝ 1096-2: 2001. The change in colorimetric parameters in reflection, on the glass side and on the layer side, is shown in Table. 12.

Table 12

<td></td><td>Sz</td><td> 8</td>

<td>ΔΕ *_ν</td><td> 3,7</td><td> 0,1</td>

<td>ΔΕ *_σ</td><td> 33,4</td><td> 0,7</td>

In addition, the comparative sample has a very strong change in appearance, in contrast to the sample according to the invention.

The excellent durability under climatic conditions provided by the photocatalytic layer allows the use of sun glazing on side 1, that is, to lay the layers outside the building.

In addition, Example 8 has a normal emissivity of 0.2 in the sense of standard ΕΝ 12898, both before and after quenching. This low emissivity makes it possible to limit the cooling of the outer surface of the window pane at night and, therefore, to achieve the effect of reducing or suppressing condensation (fogging and / or frost) when the layers are laid on side 1 of the glazing. This effect is especially pronounced in the case of an inclined double-glazed window, for example, in the roof or on the verandas.

4th series of examples.

In the table. 13 shows the composition and thickness for examples 9-12. Layering of layers is carried out in the order shown in the table, with the first line corresponding to the layer farthest from the base, and the last line corresponding to the layer in contact with the base. As in the rest of the description, the thicknesses are physical thicknesses expressed in nm.

Table 13

<img file="EA020943B1_D0007.tif" />

In the table. 14, the colorimetric and energy characteristics for Examples 9 and 10 are summarized. The designations TE, ΚΕ, q mean energy transmission, energy reflection, and absorption coefficient of solar radiation, respectively, according to the standard ΝΡ ΕΝ 410: 1998.

Table 14

<img file="EA020943B1_D0008.tif" />

- 9 020943

Laying layers 9 and 10 have a particularly neutral color in reflection from the side of the layer.

In the table. 15, the optical properties can be found for examples 11 and 12. The value ΔΕ * corresponds here to the color change in reflection from the side of the layer due to thickness fluctuations of ± 10% relative to the layer δίθ₂.

Table 15

<td rowspan="2"></td><td colspan="2"></td>

<td> 11</td><td> 12</td>

<td>TH (ΐ)</td><td> 49, 9</td><td> 54,7</td>

<td>b *</td><td> 76,0</td><td> 78,9</td>

<td>but*</td><td> -1, 1</td><td> -1, 5</td>

<td>b *</td><td> -1, 3</td><td> -2,5</td>

<td>P.1, (%)</td><td> 15,7</td><td> 8, 3</td>

<td>B *</td><td> 46,6</td><td> 34, 5</td>

<td>but*</td><td> 0,6</td><td> 2,6</td>

<td>B *</td><td> 3, 8</td><td>16 b</td>

<td>K „(%}</td><td> 20,8</td><td> 21,9</td>

<td>b *</td><td> 52,7</td><td> 53,9</td>

<td>but*</td><td> -1,4</td><td> -3, 3</td>

<td>b *</td><td> -10, 6</td><td> -2,0</td>

<td>TE (%)</td><td> 47,2</td><td> 50, 8</td>

<td>ΔΕ *</td><td> 0,1</td><td> 3,7</td>

From a comparison of ΔΕ * values, it follows that the placement of the silicon oxide layer in contact with the glass base minimizes color fluctuations in reflection due to possible fluctuations in the thickness of this silicon oxide layer. On the contrary, when the silicon oxide layer is under the photocatalytic layer, any change in its thickness entails a significant change in color.