Method for preparing a photocatalytic coating integrated into glazing heat treatment

Manufacturing method of photocatalytic coating incorporated in heat treatment of window glass

[0001] The present invention relates to a window glass (vitrages) with a photocatalytic performance coating containing at least partially crystalline titanium oxide, especially in the form of anatase.

[0002] In order to prepare such coatings, especially on glass plates, to obtain products with high optical quality, many techniques are known. For example, the sol-gel method, the pyrolysis method, and especially the vapor phase pyrolysis (CVD) method can be used. The former method involves depositing a solution of titanium dioxide precursor and then heating to form crystalline titanium dioxide in the form of anatase; In the latter method, the titanium dioxide precursor in the gas phase is optionally brought into contact with the hot substrate during the cooling process, especially with the air surface of the float glass.

[0003] In the industrial field, the cathode atomization method known from patent WO 97/10186 also has special significance. This is a technology under vacuum, which can particularly finely adjust the thickness and chemical composition of the deposited layer. In order to improve efficiency, this method is generally assisted by a magnetic field. The method can also be reactive: in this case, starting from a target that is mainly metal, here is a target based on titanium (optionally with other metals or alloys with silicon), in an oxidizing atmosphere, Ar/ The U mixture is atomized. The method can also be non-reactive, starting from a so-called ceramic target already in the form of titanium oxide (optionally an alloy). The titanium dioxide product obtained by cathode atomization is generally amorphous or poorly crystallized, and then needs to be heated to crystallize into a photocatalytically active form.

[0004] Application WO 02/24971 describes a method of depositing a partially crystalline anatase titanium dioxide coating on glass by a cathode atomization method at a relatively high working pressure of at least 2 Pa. In the first embodiment, during the deposition process, the temperature of the substrate is 220~250°C, and then annealing is performed at about 400°C if necessary; in the second embodiment, the substrate is subjected to ambient temperature Deposit and then heat for several hours at a temperature not exceeding 550°C.

[0005] In the existing knowledge, if in some cases special properties require annealing, bending, quenching or other heat treatment at higher than 600° C. or even up to 700° C., for photocatalytic Ti. ? The window glass has been studied, and the expert must deposit Ti0 after this heat treatment₂Or its precursor, and then activate it by applying a more appropriate temperature, that is, react. In particular, it is believed that a temperature exceeding 600°C is favorable for rutile Ti. The photocatalytic activity of this form of crystal is less than that of the anatase form.

[0006] At present, the inventors succeeded in obtaining photocatalytic activity and high optical quality by crystallizing titanium dioxide at the traditional glass heat treatment temperature. This crystallization can be obtained only by quenching (trempe) or other heat treatment, avoiding The subsequent supplementary operation of heating at a more moderate temperature.

[0007] Therefore, the object of the present invention is a method for producing a material with photocatalytic properties containing at least partially crystalline, especially titanium oxide in the form of anatase, characterized in that it is used at a temperature exceeding 600°C. Therefore, this preparation method can be integrated into various industrialized methods, and the special operation of crystallization at a relatively low temperature is eliminated, making these methods more simplified. This reduces the time required for these methods accordingly. Due to the use of heating that realizes two functions at the same time, the device is more simplified. Finally, the cost of these methods is reduced.

[0008] According to an embodiment that is preferred and/or particularly active, the present invention:

[0009]-The method of the present invention is carried out at over 630°C;

[0010]-Implementation of quenching and/or bending of the glass (that is, particularly capable of reaching a temperature of 700° C.).

[0011] In order to obtain excellent results in the following examples, the method of the present invention includes depositing a titanium oxide coating on the first surface of a transparent or translucent first substrate such as glass, glass ceramic (vitroceramique), and First substrate

Optionally, one or more functional laminated layers and/or functional layers are provided in advance, and their types will be described in detail below.

[0012] Some other interesting features of the method according to the invention:

[0013]-The method comprises depositing one or several functional laminates and/ on the second side of the first substrate that is transparent or translucent, or on the second side of the second substrate that is transparent or translucent Or functional layer, the types of these functional layers will also be described in detail below (in this way, the method of the present invention enables to obtain the mechanical properties obtained by heat treatment at a relatively high temperature, and can have a broader comprehensive function of the transparent Or translucent products);

[0014]-The use at a temperature exceeding 600° C. is after deposition on the first and second surfaces (however, all other embodiments in which this temperature is not applied after deposition on the second surface The present invention is not excluded, as long as it is deposited on the first side; in other words, the product deposited on the second side cannot withstand a temperature exceeding 600°C, for example, after using this temperature, the product is deposited on the second side It can only be combined with the first substrate, that is, the first substrate made of tempered glass and non-tempered glass in the case of double glazing and laminated glazing when the second surface belongs to the second substrate. The combination of the second substrate produced can withstand this temperature. In the opposite case which is also consistent with the present invention, the products deposited on the first and second sides are heated at the same time over 600°C, which may be advantageous and economical. If the second substrate exists, it will also undergo heat treatment itself);

[0015]-Deposition is carried out on the first and second faces by cathodic atomization, in which case it is advantageous to proceed in a straight line at the same time or almost at the same time in substantially the same direction and the opposite direction ( In particular, it is intended to use a magnetic field assisted cathode atomization device commonly referred to as "up and down atomization", in which the first side and the second side are horizontal, facing upward and downward, respectively, so that they are aligned with each other in a vertical average direction. The atomization cones are in contact, respectively for Tit)? Down, and for the thermal control stack, it is up). However, various other orientations of the first and second surfaces are not excluded by the present invention: for example, vertical, more or less inclined.

[0016] Another object of the present invention is a glass plate with a coating containing titanium oxide material on one side at least, characterized in that it is suitable for or withstands heat treatment above 600 ° C, such as quenching and/ Or bend while maintaining the optical quality required for photocatalytic activity and anti-fouling window glass.

[0017] First of all, heat treatment at a temperature higher than 600° C. will not affect the product, making it no longer suitable as an anti-fouling glass, and it is even unexpectedly observed. According to the above-mentioned application WO 02/24971 The heat treatment described in (such as tempering at 500°C for 1h), the photocatalytic activity of the glass obtained at the end of the heat treatment is equivalent, and in some cases even better.

[0018] The use of temperatures higher than 600° C. is not incompatible with high optical quality, which mainly involves the absence of visible defects: blurs, spots and cracks. From an industrial point of view, the average chromatic aberration AE of the reflective surface of the photocatalytic coating induced by this heat treatment is advantageously at most 2.8, preferably at most 2.3, which shows the fact that the reflectance colorimetric of the final product is different from the deposition before the heat treatment. The products are similar, AE is calculated by the following formula:

[0019] Δ E = (Δ L²+ Δ a*²+ Δ b*²）^1/2

[0020] where represents the change of the parameter caused by heating, L is the brightness, a* and b* are the chromaticity coordinates (L, a*, b* chromaticity system: the positive value of a* is towards red, the negative value is Towards green; positive values of b* are towards yellow, while negative values are towards blue; areas where a* and b* are close to 0 are colorless).

[0021] Other objects of the present invention include:

[0022]-single-layer, laminated, simple or composite window panes comprising glass panels as described above;

[0023]-a single-layer, sandwich, simple or composite window glass, wherein at least the first surface of the glass plate constituted by at least the first piece is coated with a coating of a material with photocatalytic properties obtained according to the method of the present invention.

[0024] According to other preferred characteristics of this window glass:

[0025] Under the coating with the photocatalytic performance material, the first side has one or more functional layers and/or functional layers, all of which include at least one layer that is effective for alkali metal migration of the glass Barrier layer, this migration is caused by using at a temperature exceeding 600°C (For this barrier layer, it is known that there is Si0 atomized by magnetron₂. Si₃N₄A1N, SiOC obtained by CVD, etc., as for other functional layers that can be used, there are known laminates and layers conceived as follows for the second surface, excluding hydrophilic and hydrophobic for contact with the atmosphere Floor);

[0026]-The second surface of the first glass plate or the second surface that constitutes the second glass plate has one or several functional laminate layers and/or functional layers, which are selected from, for example, solar protection and low emission Thermal control laminates, laminates or layers with optical functions such as anti-reflection, filtering light radiation, coloring, scattering, etc., anti-fouling photocatalytic materials, especially high-active layers, hydrophilic layers, and hydrophobic layers, especially Used for heating conductor mesh or conductive layer, antenna or antistatic layer, these layers can be single or combined.

[0027] Another object of the present invention is the application of such window glass as a "self-cleaning" window glass, especially as a window glass for water vapor, anti-condensation and anti-fouling, especially for double-glazed buildings. Window glass, car windshield glass, rear window glass, side window glass and other window glass, rearview mirror glass, train glass, aircraft glass, marine glass, aquarium, shop window, greenhouse, interior decoration, urban decoration (bus shelter, wall Panels, advertisements, etc.), mirrors, computer, TV, telephone display system screens, electronically controlled window glass, such as liquid crystal, electro-fluorescence and other electrochromic window glass and photoelectric glass.

[0028] The present invention is explained with the aid of examples.

Example 1

[0030] In this example, the conversion of the amorphous Tit obtained by the magnetron atomization by industrial quenching into its active form and annealing at 500° C. for 1 h for this conversion are compared.

[0031] With the aid of the photodegradation of stearic acid described in the application WO 00/75087, the photocatalytic activity after the two treatments was evaluated by infrared transmission.

[0032] Through the vapor phase cracking (CVD) as described in the application WO 01/32578, a SiOC layer with a thickness of 60 nm was deposited on 3 pieces of 4mm thick silicon-sodium-lime transparent glass samples, and the SiOC layer was atomized by a magnetron. Deposit Si0 with a thickness of 100nm on the other 3 pieces of glass₂Floor.

[0033] At 26X10^_3Under the working pressure of mbar, Ti0 of different thickness is formed on the 6 samples by magnetron atomization₂The coating is then subjected to the photocatalytic activity evaluation as described above after the above two heat treatments.

[0034] The results are summarized in Table 1 below

[0035] Table I

[0036]

<td>test#</td><td>Ti0₂Thickness (nm)</td><td>Bottom layer</td><td>TAS after quenching (10 ³cm ^χπιΐη ^x)</td><td>TAS after 1h at 500°C (10 ³cm^min ^x)</td>

<td>1</td><td>25</td><td>Si0₂</td><td>7.9</td><td>4. 7</td>

<td>2</td><td>25</td><td>SiOC</td><td>10. 2</td><td>2. 3</td>

<td>3</td><td>39</td><td>Si0₂</td><td>11. 9</td><td>6. 2</td>

<td>4</td><td>39</td><td>SiOC</td><td>3.4</td><td>7. 3</td>

<td>5</td><td>146</td><td>Si0₂</td><td>10. 5</td><td>1. 2</td>

<td>6</td><td>19</td><td>SiOC</td><td>6</td><td>3. 7</td>

[0037] Contrary to expectations, industrial quenching not only does not reduce the photocatalytic activity to an unacceptable level, but is at least comparable to the Ti0 known from the prior art specifically introduced in the already cited WO 02/24971.₂The results of the activation treatment are comparable. In fact, after quenching, the activity is no longer smaller than that of the 4# test.

[0038] Therefore, from the viewpoint of photocatalytic activity, Ti is prepared here. ? It can be hardened, even when using a barrier layer that has barrier properties to the diffusion of alkali metals in glass of normal thickness.

Example 2

[0040] Tests 1, 3, and 5 as described above, and characterized by the thickness of the resulting photocatalytic coating were 27nm and 19nm, respectively (with the same Si as in Tests 1, 3 and 5.? Barrier underlayer and the same Ti0₂The tests 7 and 8 of the preparation conditions) were used as the measurement objects of the average chromaticity change value AE of the coating surface reflection caused by industrial quenching. In the chromaticity system, the meaning of each parameter L, a*, b* and the formula for calculating AE from , Ab* are as described above.

[0041] The results are summarized in Table II below.

[0042] Table II

[0043]

<td>test#</td><td>AL</td><td>Δ a*</td><td>Ab*</td><td>ΔΕ</td>

<td>1</td><td>1. 02</td><td>0. 23</td><td>-0. 46</td><td>1. 14</td>

<td>3</td><td>-0. 08</td><td>0. 77</td><td>-2. 10</td><td>2.24</td>

<td>5</td><td>1. 40</td><td>-0. 47</td><td>0. 91</td><td>1. 73</td>

<td>7</td><td>1. 70</td><td>-0. 57</td><td>0. 04</td><td>1. 79</td>

<td>8</td><td>1. 39</td><td>-1. 15</td><td>-2. 09</td><td>2. 76</td>

[0044] The average chromaticity change value is relatively low, in some cases even ideally less than 2, which indicates that the color change of the photocatalytic coating surface reflection of all the coatings is very small after being industrially quenched. In the quenching process, an undesirable quenched product whose reflection chromaticity changes too much will not be obtained. This makes it easy to imagine the final color before quenching.

Example 3

[0046] This embodiment relates to a double-layer glass composed of two glass plates with a thickness of 4 mm, and an air layer with a thickness of 15 mm is filled in between. In this embodiment and the following embodiments, the double-glazed surface 2, that is, the surface of the glass plate closest to the outside atmosphere (not the surface facing the interior of the building) that is in contact with the air gap is coated with A stack of thermal control layers manufactured by magnetron atomization. This method is particularly practical when the properties of the deposited layers vary widely by changing their thickness and precise control on an industrial scale.

[0047] Here, the laminate is low-emissive, that is, reflects thermal infrared (wavelength approximately 10 μm) and is suitable for maintaining

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Indoor heat.

[0048] From an optical point of view, the thermal control stack on the surface 2 and the photocatalyzed Ti0 obtained by magnetron atomization₂And Si0 that has barrier properties to the diffusion of alkali metals in the surface 1 in contact with the outside atmosphere₂The combination of laminated layers composed of the bottom layer was studied.

[0049] In the following, X and Y are used to denote the same low-emission stack as in Example 2 of EP 0 718250 A2, except that the thickness of layer is changed to 25 nm, and layer is changed to 19 nm and layer Change to 29nm.

[0050] The composition of the following 4 types of window glass was tested, except that the outer glass plate was defined as follows:

[0051] 3a: 4mm glass/36nmSi₃N₄/X

[0052] 3b: 18nmTiO₂/15OnmSiO₂/4mm glass/X

[0053] 3c: 18nmTi0₂/75nmSi0₂/9nmSi₃N₄/63nmSi0₂/4mm glass/X

[0054] 3d: (the same photocatalytic laminate as 3b).../4mm glass/Y

[0055] In this example and in the following examples 4 to 7, all laminates are subjected to industrial quenching. The optical properties of the window glass are the transmittance, the "inside" of the building (that is, the double-glazed surface 4, as pointed out above, of which only surfaces 1 and 2 are functionalized) reflectance, and the "outside" of the building ( Surface 1: Glass or Ti0₂) The reflectance was evaluated (light transmittance and reflectance Ji and R_lThe unit of is %, and the chromaticity coordinates a* and b* for transmission and reflection on both sides of the window glass are as described above). The results are reported in the table below.

[0056] Table III. 1: Transmission

[0057]

<td>Window glass#</td><td>TL</td><td>* a</td><td>b*</td>

<td>3a</td><td>78.9</td><td>-2. 3</td><td>0. 8</td>

<td>3b</td><td>75. 0</td><td>-2. 0</td><td>2. 0</td>

<td>3c</td><td>76.8</td><td>-2. 4</td><td>1. 2</td>

<td>3d</td><td>74. 1</td><td>-2. 5</td><td>2. 4</td>

[0058] Table III. 2: Internal reflection

[0059]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>3a</td><td>12. 2</td><td>0. 2</td><td>-2. 6</td>

<td>3b</td><td>15. 7</td><td>-1. 1</td><td>-5. 3</td>

<td>3c</td><td>14. 1</td><td>0. 2</td><td>-3. 6</td>

<td>3d</td><td>16. 0</td><td>0. 5</td><td>-6. 0</td>

[0060] Table III. 3: Outside reflection

[0061]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>3a</td><td>11. 6</td><td>0. 0</td><td>-5. 8</td>

<td>3b</td><td>16. 0</td><td>-1. 0</td><td>-8. 1</td>

<td>3c</td><td>13. 9</td><td>0. 4</td><td>-6. 4</td>

<td>3d</td><td>15. 8</td><td>0. 6</td><td>-8. 7</td>

[0062] A comparison of the window glass 3a and 3b shows how the addition of the photocatalytic coating easily interferes with the optical properties of the window glass: it can therefore be seen that the jig is reduced, the% on both sides is increased, and The reflection chromaticity on both sides of the window glass shifts to blue-green ('and b* are negative values).

[0063] By comparing the window glass 3c with the window glass 3b, a part of the lost T is recovered_L, And the two R_LThe value is again advantageously close to the window glass 3a, as is the chromaticity value of its reflection.

Example 4

[0065] The method of Example 3 was adopted for the following window glass (the average wavelength of the laminated reflection on the surface 2 is equivalent to about lum of sunlight). In this embodiment, X and Y are used to represent the sun protection laminate of Saint-Gobain Glass France under the trade name SGG Coollite ST ® 108, respectively, by multiplying the thickness of the last layer on the side close to the glass substrate by 3. 7, and the thickness of the distal end is multiplied by 2/3 to get the stack:

[0066] 4a: 6mm glass/X

[0067] 4b: 18nmTiO₂/15OnmSiO₂/6mni glass/X

[0068] 4c: 18nmTi0₂/50nmSi0₂/12nmSi₃N₄/71 nmSi0₂/6mni glass/X

[0069] 4d: the same photocatalytic coating as 4b/6mm glass/Y

[0070] In this embodiment and in the following embodiments, the window glass is composed of two glass plates with a thickness of 6 mm and an air gap with a thickness of 12 mm inserted therein.

[0071] The results are summarized in the table below.

[0072] Table IV. 1: Transmission

[0073]

<td>Window glass#</td><td>TL</td><td>* a</td><td>b*</td>

<td>4a</td><td>6. 6</td><td>2. 1</td><td>6. 8</td>

<td>4b</td><td>6. 4</td><td>2. 2</td><td>7. 2</td>

<td>4c</td><td>6. 4</td><td>2. 2</td><td>6. 7</td>

<td>4d</td><td>8. 5</td><td>1. 6</td><td>6. 6</td>

[0074] Table IV. 2: Internal reflection

[0075]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>4a</td><td>34. 4</td><td>-2. 4</td><td>13. 1</td>

<td>4b</td><td>34. 4</td><td>-2. 4</td><td>13. 1</td>

<td>4c</td><td>34. 4</td><td>-2. 4</td><td>13. 1</td>

<td>4d</td><td>28. 2</td><td>-1. 0</td><td>13. 8</td>

[0076] Table IV. 3: External reflection

[0077]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>4a</td><td>39. 4</td><td>-3. 0</td><td>1. 9</td>

<td>4b</td><td>41. 5</td><td>-3. 0</td><td>0. 4</td>

<td>4c</td><td>41. 3</td><td>-3. 1</td><td>1. 8</td>

<td>4d</td><td>39. 4</td><td>-3. 1</td><td>1. 9</td>

[0078] Here, Ti0 is added₂Able to affect T_L, Which prompted Ti0₂ (4b)/The yellow reflection on the outside of the glass (4a) is slightly reduced.

[0079] The change of the solar protection laminate (4d) leads to an increase in ΊΥ, a substantial decrease in the outer %, and a slight increase in the reflected yellow.

Embodiment 5

[0081] Repeat Example 4, where X and Y respectively represent the solar protection laminate of Saint-Gobain Glass France under the trade name SGG Coollite ST ® 120. The laminate is the same, except that the thickness of the layer close to the glass substrate is multiplied by Take:

[0082] 5a: 6mm glass/X

[0083] 5b: 18nmTiO₂/15OnmSiO₂/6mni glass/X

[0084] 5c: 18nmTi0₂/68nmSi0₂/ 10nmSi₃N₄/69nmSi0₂/6mm glass/X

[0085] 5d: the same 5b/6mm glass/Y

[0086] Table V. 1: Transmission

[0087]

<td>Window glass#</td><td>TL</td><td>* a</td><td>b*</td>

<td>5a</td><td>17. 2</td><td>-2. 3</td><td>-3.9</td>

<td>5b</td><td>16. 5</td><td>-2. 2</td><td>-3. 2</td>

<td>5c</td><td>16. 8</td><td>-2. 3</td><td>-3. 9</td>

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<td>5d</td><td>17. 0</td><td>-2. 2</td><td>-3.9</td>

[0088] Table V. 2: Internal reflection

[0089]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>5a</td><td>29. 5</td><td>-0. 3</td><td>13. 7</td>

<td>5b</td><td>29. 7</td><td>-0. 3</td><td>13. 4</td>

<td>5c</td><td>29. 6</td><td>-0. 3</td><td>13. 6</td>

<td>5d</td><td>31. 1</td><td>-0. 5</td><td>12. 8</td>

[0090] Table V. 3: Outside reflection

[0091]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>5a</td><td>32. 5</td><td>-1. 5</td><td>-1. 1</td>

<td>5b</td><td>34. 9</td><td>-1. 6</td><td>-2. 4</td>

<td>5c</td><td>33. 8</td><td>-1. 3</td><td>-1. 0</td>

<td>5d</td><td>32. 4</td><td>-1. 5</td><td>-1. 0</td>

[0092] Compared with 5b and 5a, 5c recovers a part of the lost T_LAnd two R-especially, the color reflected on the two surfaces is completely restored, and the same is true for the slightly increased coloring neutrality.

[0093] For 5d, to increase Ji, the reflection on the inner side is slightly increased (slightly worse), while the reflection on the outer side (Ti0₂) The reflection is lower than the R of the outer side (glass) of 5a_lSmaller level (better).

Example 6

[0095] Repeat the previous embodiment for the following window glass, where X and Y respectively represent the sun protection laminate of Saint-Gobain Glass France under the trade name SGG Coollite ST ® 136. The laminate is the same, except that the glass substrate is close to The thickness of the end and the distal end layer are multiplied by 1.7 and 0.774, respectively:

[0096] 6a: 6mm glass/X

[0097] 6b: 18nmTiO₂/15OnmSiO₂/6mni glass/X

[0098] 6c: 18nmTi0₂/66nmSi0₂/1 OnmSi₃N₄/57nmSi0₂/6mni glass/X

[0099] 6d: The same photocatalytic laminate as 6b/6mm glass/Y

[0100] Table VI. 1: Transmission

[0101]

<td>Window glass#</td><td>TL</td><td>* a</td><td>b*</td>

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[0102]

[0103]

[0104]

<img file="CN1826296B_D0001.tif" />

[0105]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>6a</td><td>21. 4</td><td>-1. 2</td><td>-6.4</td>

<td>6b</td><td>24. 8</td><td>-1. 6</td><td>-7. 5</td>

<td>6c</td><td>23. 4</td><td>-1. 1</td><td>-6. 3</td>

<td>6d</td><td>21. 1</td><td>-1. 4</td><td>-6. 2</td>

[0106] When 6a is compared with 6b, the characteristic is that the% of the outside of the window glass increases, and the degree of increase is smaller than the degree of increase in the chromaticity of the second side relative to the first side.

[0107] Through the optimization of the photocatalytic laminate 6c, a part of the lost T" is restored while the outer reflection color is restored (the same for the more neutral chromaticity than 6a), so that the R on the same side_lreduce.

[0108] By changing the solar protection laminate 6d, the outer side (Ti0₂The% of) is reduced to a level even lower than that of the glass surface 6a, and the yellow component of the reflection color on the inner side of the window glass is also lower than that of the three other window glass.

Example 7

[0110] Repeat the previous example with the following window glass, where X and Y represent Saint-Gobain Glass, respectively

The solar protection laminate under the trade name of SGG Coollite ST ® 150 from France, the laminate is the same, except that the layer close to the glass substrate is removed, and the thickness of the middle layer is multiplied by 1.5, and the thickness of the distal layer is multiplied by 0. 68: [0111] 7a: 6mm glass/X

[0112] 7b: 18nmTiO₂/15OnmSiO₂/6mni glass/X

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[0113] 7c: 18nmTi0₂/64nmSi0₂/13nmSi₃N₄/50nmSi0₂/6mni glass/X

[0114] 7d: The same photocatalytic laminate as 7b/6mm glass/Y

[0115] Table VII. 1: Transmission

[0116]

<td>Window glass#</td><td>TL</td><td>* a</td><td>b*</td>

<td>7a</td><td>45. 7</td><td>-2. 4</td><td>-1. 3</td>

<td>7b</td><td>43. 5</td><td>-2. 1</td><td>-0. 3</td>

<td>7c</td><td>44. 4</td><td>-2. 3</td><td>-1</td>

<td>7d</td><td>33. 4</td><td>-2. 1</td><td>-0. 4</td>

[0117] Table VII. 2: Internal reflection

[0118]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>7a</td><td>21. 4</td><td>-1. 0</td><td>1. 5</td>

<td>7b</td><td>22. 6</td><td>-1. 3</td><td>0. 4</td>

<td>7c</td><td>22. 1</td><td>-1. 1</td><td>1. 1</td>

<td>7d</td><td>26. 0</td><td>-1. 1</td><td>2. 1</td>

[0119] Table VII. 3: External reflection

[0120]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>7a</td><td>14. 3</td><td>-1. 1</td><td>-7. 2</td>

<td>7b</td><td>18. 4</td><td>-1. 8</td><td>-8. 8</td>

<td>7c</td><td>16. 7</td><td>-1. 1</td><td>-7. 3</td>

<td>7d</td><td>17. 5</td><td>-1. 2</td><td>-6. 8</td>

[0121] This particularly shows that the reflected color of the outer side 7c with respect to 7a is almost completely restored.

Example 8

[0123] This embodiment relates to the so-called "quatre saisons" laminate, which is solar-proof and low-emission at the same time, and is a product of the trade name Planistar® of Saint-Gobain Glass France. It is different from the thermal control laminate of the previous embodiment, but similar to the following embodiment, it has not undergone industrial quenching, so if necessary, it is optional

CN 1826296 Β

With TiO₂The coating and barrier layer are quenched before deposition on the glass plate.

[0124] Test the following window panes:

[0125] 8a: 6mm glass/Planistar®

[0126] 8b: 18nmTiO₂/15OnmSiO₂/6mm glass/Planistar ®

[0127]

[0128]

[0129]

8c: 18nmTi0₂/68nmSi0₂/8nmSi₃N₄/58nmSi0₂/6mm glass/Planistar ® Table VIII. 1: Transmission

[0132]

[0133]

[0130]

[0131]

<img file="CN1826296B_D0002.tif" />

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>8a</td><td>11. 1</td><td>-2. 6</td><td>-2. 6</td>

<td>8b</td><td>16. 3</td><td>-1. 2</td><td>-4. 2</td>

<td>8c</td><td>13. 9</td><td>-2. 3</td><td>-3. 2</td>

The window glass 8c has restored the color reflected on the inside and outside of 8a relative to 8b, here R_lRelative to 8b

[0134] The lower is slightly more pronounced.

Example 9

[0136] This thermal control laminate is a product of the trade name SKN ® 154 from Saint-Gobain Glass France.

Test the window glass as follows:

[0137] 9a: 6mm glass/SKN ® 154

[0138] 9b: 18nmTiO₂/15OnmSiO₂/6mm glass/...same 9a

CN 1826296 Β

[0139] 9c: 18nmTi0₂/68nmSi0₂/8nmSi₃N₄/58nmSi0₂/6mm glass/ same 9a

[0140] Table IX. 1: Transmission

[0141]

<td>Window glass#</td><td>TL</td><td>* a</td><td>b*</td>

<td>9a</td><td>49. 3</td><td>-7. 9</td><td>2. 7</td>

<td>9b</td><td>47. 0</td><td>-7. 5</td><td>3. 5</td>

<td>9c</td><td>47. 8</td><td>-7. 7</td><td>3. 0</td>

[0142] Table IX. 2: Internal reflection

[0143]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>9a</td><td>23. 0</td><td>0. 7</td><td>5. 9</td>

<td>9b</td><td>24. 4</td><td>-0. 2</td><td>4. 9</td>

<td>9c</td><td>24. 0</td><td>0. 1</td><td>5. 4</td>

[0144] Table IX. 3: External reflection

[0145]

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>9a</td><td>19. 2</td><td>-3. 1</td><td>-9. 2</td>

<td>9b</td><td>22. 8</td><td>-3. 2</td><td>-9. 9</td>

<td>9c</td><td>21. 6</td><td>-2. 9</td><td>-9. 3</td>

[0146] Here, it is particularly obvious that the middle% between the other two window glasses is obtained on the outside of 9c, and the reflected blue component is different from the absence of Ti0.₂The 9a is almost the same.

Example 10

[0148] Tests were performed on laminated glass, which is also traded by the company under the trade name SKN ® 165B, and more specifically the following window glass:

[0149] 10a: 6mm glass/SKN ® 165B

[0150] 10b: 18nmTiO₂/15OnmSiO₂/6mm glass/...same 10a

[0151] 10c: 18nmTi0₂/69nmSi0₂/9nmSi₃N₄/49nmSi0₂/6mm glass/...same 10a

[0152] Table X. 1: Transmission

[0153]

<td>Window glass#</td><td>TL</td><td>* a</td><td>b*</td>

CN 1826296 Β

[0156]

[0157]

[0154]

[0155]

<img file="CN1826296B_D0003.tif" />

<td>Window glass#</td><td>RL</td><td>* a</td><td>b*</td>

<td>10a</td><td>15. 7</td><td>-2. 2</td><td>-9. 8</td>

<td>10b</td><td>19. 6</td><td>-2. 6</td><td>-10. 5</td>

<td>10c</td><td>17. 9</td><td>-1. 9</td><td>-10. 1</td>

Example 11 Example 5 of the patent EP 0 850204B1 was repeated, and an alkali metal migration with a thickness of 50 nm was formed on a glass plate.

[0158]

[0159] Shift the SiOC coating with barrier properties, and cover it with 15nm Ti0 by CVD₂Photocatalytic layer.

[0160] Through the photodegradation of stearic acid, and then through the infrared transmission evaluation as described above, its photocatalytic activity is 9X 10 ^ / cm · min, after industrial quenching is 7X 10 ^ / cm · min, which is equivalent It maintains its functionality in a wide range and in satisfactory proportions.

[0161] The present invention makes it possible to manufacture window glass that can be quenched and has a highly active anti-fouling photocatalytic coating. Under the best industrial conditions, users can easily determine the level of light transmission and reflection, as well as the transmission and The color characteristics of the reflection are adjusted to the desired level.