Process for the production of photocatalytic coatings on substrates

A method of manufacturing photocatalytic coatings on substrates

This invention relates to a method for producing active photocatalytic coatings on substrates; in particular, but not exclusively, it relates to a method for manufacturing glasses with active photocatalytic and other similar coatings.

A known method of deposition on substrates, including glass substrates, of thin single or multilayer coatings that have various properties. One of the properties of particular interest is photocatalytic activity, which occurs as a result of the photo-generation of a hole-electron semiconductor pair when a semiconductor is exposed to light of an appropriate wavelength. A hole-electron pair can form in sunlight and in a humid atmosphere can react with the formation of hydroxyl and peroxyl radicals on the surface of a semiconductor. Radicals oxidize organic pollution on the surface. This property is used to obtain self-cleaning surfaces, in particular, self-cleaning window panes.

An effective photocatalyst can be titanium dioxide, which can be deposited on a substrate to obtain a transparent coating having the properties of photocatalytic self-cleaning. Photocatalytic coatings based on titanium oxide are described in EP 0 901 991 A2, TO 97/07069, TO 97/07069, TO 97/10186, TO 98/41480, in Al! 735 о £ 187 * Е1ес (gosyet1sa1 5os1e1u Meijp§ (Kepo, Νν, 95-1, p. 1102) and in the journal \ε \ ν 8с1пйз1 (26 Aigiz1 1995, p. 19). No. 98/06675 describes a chemical vapor deposition method in which titanium oxide coatings are deposited at high speed onto hot flat glass using a gas mixture of titanium chloride and an organic compound that is an oxygen source for forming the titanium oxide coating.

It was previously believed that in order to obtain good photocatalytic activity, relatively thick titanium oxide coatings should be deposited. For example, AUO 98/41480 states that self-cleaning active photocatalytic coatings must be thick enough to provide an acceptable level of activity, and the preferred coating thickness is at least about 200, preferably at least about 500 A (measured the thickness of the titanium oxide coatings obtained in the Examples was in the range from 400 to 2100 A).

However, the disadvantage of relatively thick titanium oxide coatings is that they have a high degree of reflection of visible light and, therefore, a relatively low light transmission. This drawback is described in the aforementioned article in the magazine Νβ \ ν 8c1epbz1 regarding coated windscreens, where it is proposed to reduce the effect of strong reflection to cover the dashboard with black velvet or other material that does not reflect light on the coated windshield.

The above-mentioned application EP 0 901 991 A2 relates to photocatalytic glass panels coated with titanium dioxide of a particular crystalline structure, which is characterized by the presence of special peaks in its X-ray diffraction pattern. In the description, coatings of various thicknesses are considered (the coating thickness in the Examples was in the range from 20 nm to 135 nm, while thinner coatings had less photocatalytic activity than thicker coatings). The description also contemplates various deposition temperatures ranging from a minimum of 300 ° C. to a maximum of 750 ° C., temperatures from 400 ° C. to 600 ° C. being preferred, and in all Examples of the invention, a layer of titanium dioxide was deposited at a temperature within this preferred range or below.

The authors of this application found that by deposition of titanium oxide coatings at higher temperatures, in particular, temperatures above 600 ° C, it is possible to obtain coatings of a given thickness with increased photocatalytic activity, while the same photocatalytic characteristics can be obtained with a smaller coating thickness. It is significant that such thinner coatings reduce the reflection of visible light and, obviously, due to the higher temperature of their deposition, have increased wear resistance, in particular, increased resistance to abrasion and cyclic temperature loads in a humid atmosphere.

Thus, the present invention relates to a method for manufacturing substrates with an active photocatalytic coating, which comprises depositing a titanium oxide coating on a substrate surface by bringing the substrate surface in contact with a fluid mixture containing a titanium source and an oxygen source, wherein said substrate has a temperature of at least 600 ° C, due to which the coated surface of the substrate has a photocatalytic activity of more than 5 x 10 '³cm ^ min. '¹and the reflection of visible light measured on the coated side is 35% or less.

Preferably, the substrate has a temperature of from 625 to 720 ° C, more preferably from 645 to 720 ° C.

It is advisable if the fluid mixture includes titanium chloride as a source of titanium, as well as an ester other than methyl ester. Thus, according to a preferred embodiment, a method of manufacturing substrates with an active photocatalytic coating comprises depositing a titanium oxide coating with a thickness of less than 40 nm by contacting the surface of the substrate with a fluid mixture containing titanium chloride and an ester other than methyl ester.

The method can be carried out under conditions when the surface of the substrate is in contact with the fluid mixture at a temperature of the substrate from 600 to 750 ° C.

Preferably, the ester is an alkyl ester containing an alkyl group with β-hydrogen (the alkyl group of the alkyl ester is a group derived from alcohol in the synthesis of the ester, and β hydrogen is hydrogen bonded to the carbon atom β relative to the oxygen of the ester bond in the ester ) Preferably, the ester is a carboxylate ester.

Suitable esters may be alkyl esters having an Cg-Csu alkyl group, however, preferably the ester is an alkyl ester having an C alkyl group₂-FROM₄.

Preferably, the ester is a compound of the formula K.-C (O) Ο-Ο (Χ) (Χ ') - <3 (Υ) (Υ') - Κ- ', where K and K.' represent hydrogen or an alkyl group, X, X ', Υ and Υ' represent monovalent substituents, preferably alkyl groups or hydrogen atoms, and where at least one of the groups Υ and Υ 'represents hydrogen.

Suitable esters that can be used in the method of this invention include: ethyl format, ethyl acetate, ethyl propionate, ethyl butyrate, η-propyl format, η-propyl acetate, p-propyl propionate, propyl butyrate, isopropyl format, isopropyl acetate, isopropyl propionate, isopropyl butyl butyrate β-butyl acetate and ί-butyl acetate.

Preferably, the ester is ethyl ether, more preferably the ether is ethyl format, ethyl acetate or ethyl propionate. Most preferably, the ester is ethyl acetate.

The fluid mixture may be liquid, in particular dispersed in the form of fine dust (this is often referred to as spray deposition), but preferably the fluid mixture is gaseous. The deposition method, carried out using the initial gaseous mixture, is often called chemical vapor deposition (CUL Cesh1ca1 Uarog Lerozyup). Preferably, a laminar flow is used in the LMS, although a LPS method with a turbulent flow can also be used.

Deposition by the method can be carried out on substrates of various sizes, including sheet substrates, in particular, format sheets of glass, or preferably on a continuous tape of glass directly in the manufacturing process of float glass. Thus, preferably, the method is carried out online, i.e., directly during the manufacturing of float glass, and the glass ribbon is the substrate. If the method is carried out during the production process, then it is preferably performed on a glass tape when it is in the float bath.

The advantage of implementing the method in the on-line mode is that the coating obtained in this mode is more wear-resistant, in particular, it has an increased abrasion resistance and a higher chemical resistance.

Although an on-line deposition method is preferred, other deposition methods that are carried out at substantially atmospheric pressure are also possible.

In a most preferred embodiment, the proposed method for manufacturing glass with a wear-resistant active photocatalytic coating comprises depositing an active photocatalytic titanium oxide layer onto the surface of the glass substrate by bringing the surface of the substrate having a temperature in the range of 645-720 ° C, preferably in the range of 670-720 ° C, contact with a fluid mixture containing a source of titanium.

As noted above, the authors found that the deposition of titanium oxide at high temperature can be obtained coatings with relatively high photocatalytic activity for their thickness, and since coatings with a small thickness give a weaker reflection, the invention also relates to new products in which High photocatalytic activity is well combined with moderate or low light reflection.

Thus, in another aspect, the present invention provides an active photocatalytic coating product comprising a substrate with an active photocatalytic titanium oxide coating deposited on one of its surfaces, characterized in that the coated surface of the substrate has a photocatalytic activity of greater than 5 x 10 '³ cm ^ min.¹and the fact that the reflection of the visible coated substrate measured on the coated side is 35% or less.

High photocatalytic activity is useful because the amount of contaminants (including dirt) on the coated surface of the active photocatalytic coated substrate will decrease faster than on substrates with relatively low photocatalytic activity. Besides

Moreover, with high photocatalytic activity, faster removal of surface contaminants is achieved at low levels of ultraviolet light intensity.

Photocatalytic activity in the context of the present description is determined by measuring the decrease in the integrated absorbance of the infrared absorption peaks corresponding to the CH bands of a thin film of stearic acid deposited on a coated substrate when exposed to UV radiation from a UV lamp having an intensity of about 32 W / m² the coated substrate surface has a peak wavelength of 351 nm. Stearic acid can be applied to the coated substrate by centrifuging a solution of stearic acid in methanol, as described below.

Preferably, the coated surface of the substrate has photocatalytic activity greater than 1 x 10 '² cm ^ min. '¹more preferably

one 1 over 3x10 'cm' min. ' .

With weak reflection of visible light, fewer distractions arise than with high reflection, which is important, especially in the case of glass substrates, since with low reflection of visible light, high light transmission is ensured, which is important when using glass in architectural structures and especially in automobiles.

Preferably, the reflection of the visible coated substrate measured on the coated side is 20% or less, more preferably 17% or less, and most preferably 15% or less.

In most embodiments, the coated substrate will be substantially transparent, and in a preferred embodiment, the substrate is a glass substrate. Typically, the glass base is made of sodium-calcium-silicate glass.

If the substrate is made of sodium-calcium-silicate glass or contains another alkali metal ion, then preferably between the surface of the substrate and the active photocatalytic titanium oxide coating there is an underlying layer blocking the alkali metal ion. This reduces the ability of alkali metal ions to migrate from the substrate to the active photocatalytic titanium oxide coating, which is important due to the known ability of alkali metal ions to poison semiconductor oxide coatings and reduce their activity.

The underlying alkali metal ion blocking layer may comprise metal oxide, but preferably the alkali metal ion blocking layer is a silicon oxide layer. Silica can be silica, but it does not have to be stoichiometric and may contain inclusions such as carbon (in this case it is often called oxycarbide and precipitated as described in OV 2,199,848B) or nitrogen (silicon oxynitride).

It is advisable if the underlying layer blocking the alkali metal ion is so thin that it does not significantly affect the optical properties of the coating, in particular, does not reduce the transparency of the coated substrate or does not create interference patterns upon reflection or transmission. A suitable thickness range will depend on the properties of the material used to form the layer blocking alkali metal ions (in particular, on its refractive index), but usually the underlying layer blocking alkali metal ions has a thickness of less than 60 nm, preferably less than 40 nm. If this layer is present, it should always be thick enough to reduce or block the migration of alkali metal ions from the glass into the titanium oxide coating.

An advantage of the present invention is that the thickness of the active photocatalytic titanium oxide coating can be sufficiently small (which provides a weak reflection of the visible light of the coated substrate), however, the coated substrate has high photocatalytic activity. Preferably, the titanium oxide coating has a thickness of 30 nm or less, more preferably 20 nm or less, and most preferably the titanium oxide coating has a thickness in the range of 2 nm to ~ 20 nm.

An advantage of the present invention is also that in the deposition of titanium oxide coatings less initial mixture is required, and the layers can be deposited in a relatively short time. A thin titanium oxide coating is also less likely to cause interference patterns when reflected or transmitted. However, a particular advantage is that the titanium oxide coating has a low reflectance of visible light, which is especially important when the substrate is glass. Typically, the thickness of the titanium oxide coating is determined based on the required transmittance of the coated glass.

Preferably, the coated surface of the substrate has a contact angle with water equal to or less than 20 °. Freshly made or cleaned glass has a hydrophilic surface (a wetting angle with water of less than 40 ° means a hydrophilic surface), but organic impurities quickly adhere to the surface, increasing the wetting angle. A particular advantage of the coated substrates (and especially the coated glasses) of the present invention is that irradiating the appropriate wavelength with UV light even of the contaminated coated surface will reduce the wetting angle by reducing the amount or destruction of these contaminants. An additional advantage is that water will spread over a surface with a smaller wetting angle, which ensures a less distracting effect of water droplets on the surface (for example, from rain) and the washing away of dirt and other substances that were not destroyed due to the photocatalytic activity of the surface. The contact angle with water is the angle formed by the meniscus of the water drop on the glass surface, and can be determined in a known manner by measuring the diameter of a water drop of known volume on the glass surface and calculated iteratively.

Preferably, the coated substrate has a haze factor of 1% or less, which is also useful since this provides good visibility through the transparent coated substrate.

In preferred embodiments, the coated surface of the substrate is abrasion resistant so that the coated surface remains photocatalytically active after 300 strokes in a European standard abrasion test. Preferably, the coated surface retains photocatalytic activity after 500 strokes in the abrasion test according to the European standard, and more preferably after 1000 strokes in the abrasion test according to the European standard.

This is an important property since self-cleaning coated articles of the present invention will often use the coated surface outward (for example, glass whose coated surface is used as the outer surface of the window) and the coating will undergo abrasion.

The European standard of the abrasion test for B δ ΕΝ 1096 Paradise 2 (1999) includes the reciprocating movement of the felt presser slide at a given speed and pressure on the surface of the sample.

In the context of this description, a coated substrate will be considered to have retained photocatalytic activity if, after abrasion tests according to the European standard, irradiation with ultraviolet light (for example, with a peak wavelength of 351 nm) reduces the contact angle with water to below 15 °. This contact angle after abrasion of the coated substrate is usually achieved in less than 48 hours of irradiation at an intensity of about 32 W / m at the coated surface of the substrate.

Preferably, the coated substrate has a haze coefficient of 2% or less after abrasion tests according to European standard.

The wear-resistant coated substrates of this invention can also be resistant to cyclic moisture resistance tests (which simulate atmospheric effects). Thus, in preferred embodiments, the coated surface of the substrate is resistant to cyclic moisture resistance tests so that the coated surface remains photocatalytically active after 200 cycles. In this specification, cyclic moisture resistance tests are tests in which a coating is thermally cycled in a cycle of 35 ° C 75 ° C-35 ° C for 4 hours at almost 100% relative humidity. A coated substrate is considered to have retained photocatalytic activity if, after testing, irradiation with ultraviolet light reduces the contact angle with water to below 15 °.

In a further preferred embodiment, the present invention provides wear-resistant coated photocatalytically active glass, which is a glass substrate having a coating on one of its sides, said coating comprising a base layer blocking an alkali metal ion, and a photocatalytically active titanium oxide layer, and coated the surface of the substrate is abrasion resistant so much that the coated surface remains photocatalytically active after 300 strokes in the abrasion test according to the European standard. In this embodiment, the coated glass preferably reflects 35% or less of visible light from the coated side, and the photocatalytically active titanium oxide layer preferably has a thickness of 30 nm or less. It was unexpectedly found that thin coatings are resistant to abrasion, although it was previously assumed that only relatively thick coatings can have good wear resistance.

In a further embodiment, the invention provides coated glass comprising a glass substrate that has an active photocatalytic titanium oxide coating on one of its sides, characterized in that the coated glass surface has a photocatalytic activity of more than 4 x 10 '² cm ^ min. '¹preferably more than 6 x 10 '² cm ^ min.¹ and more preferably more than 8 x 10 '² cm ^ min. '¹, and the fact that coated glass reflects less than 20% of visible light when measured on the coated side.

The coated products of this invention are used in many fields, for example, in glazing modules, including multi-panel glazing modules, which comprise a first glazing panel in the form of coated glass and a second glazing panel with an air gap between them, or in the form of laminated glass containing a first glass layer of coated glass, a polymer intermediate layer (e.g., polyvinyl butyral) and a second glass layer.

The coated products of this invention can not only be used as self-cleaning products (in particular, self-cleaning window glasses), but can also be useful in reducing the concentration of atmospheric pollution. For example, coated glass when exposed to ultraviolet light (including ultraviolet radiation contained in sunlight) can destroy atmospheric pollution such as nitrogen oxides, ozone and organic pollutants adsorbed on the surface of the coated glass. This is especially important when used outdoors in built-up areas (for example, on city streets), where the concentration of organic pollutants can be relatively high (especially in intense sunlight), but in this case it is required that the glass surface area is large enough. In other cases, coated glass (with a coated surface facing inward) can be used to reduce the concentration of air pollution inside buildings, especially in office buildings that have a relatively high concentration of pollution.

The invention is further illustrated, but not limited, by the following figures.

In FIG. 1 shows a graph of photocatalytic activity versus titanium oxide layer thickness for coated glass made by the method of the invention.

In FIG. 2 shows a plant for the chemical deposition of coatings according to the invention from the vapor phase directly in the glass manufacturing process.

Presented in FIG. 1 coated glass was obtained directly in the manufacturing process, i.e., in the on-line mode, by the method of SUE described below in the Examples. Circles 1 refer to titanium oxide layers deposited using titanium tetrachloride as a starting titanium component, and crosses 2 refer to titanium oxide layers deposited using titanium tetraethoxide as a starting titanium component.

Coating layers can be applied on-line to a glass substrate by chemical vapor deposition during glass production. In FIG. 2 shows the installation, indicated by the general position 10, suitable for the operational production of glass products with a coating according to this invention, including a float section 11, lehr 12 and a cooling section 13. The float section 11 has a bottom 14 with a bath of molten tin 15, a lid 16, side walls (not shown) and end walls 17, which together form a sealed structure containing a closed zone 18, which maintains a non-oxidizing atmosphere that prevents oxidation of tin in the bath 15 . During the operation of the installation 10, molten glass 19 is poured into the hearth 20 and from there it flows under the dosing wall 21 down onto the surface of the tin bath 15, forms a ribbon of float glass 37, which is removed using tear-off rollers 22 and transported through the scraper 12 and then through the section cooling 13.

The non-oxidizing atmosphere in the float section 11 is maintained by supplying a suitable gas, for example, a gas containing nitrogen and 2% (vol.) Hydrogen, to zone 18 through pipelines 23 that are connected to a manifold 24. Non-oxidizing gas is supplied to zone 18 from pipelines 23 at a speed sufficient to compensate for gas losses (part of the non-oxidizing atmosphere flows from zone 18 under the end walls 17), and to maintain a slight excess pressure with respect to the environment. The tin bath 15 and the enclosed zone 18 are heated by radiation from the heaters 25 installed above. The heating zone 18 is generally maintained at a temperature of about 1330-1400 ° P (721-760 ° C). The atmosphere in Lehr 12 is usually air, and the cooling zone is generally open to the outside. The glass is blown with ambient air using fans 26.

Installation 10 also includes devices 27, 28, 29 and 30 for coating located in series in the float zone 11 above the ribbon of float glass 37. The source gaseous mixtures for the individual coating layers are supplied to the respective coating devices, which, in turn, direct source gaseous mixtures on the hot surface of the float glass tape 37. The temperature of the float glass tape 37 has the highest value at the location of the coating device 27 closest to the hearth 20, and the lowest value at the location of the coating device 30 closest to the lehr 12.

The invention is further illustrated by Examples in which coatings were applied by chemical vapor deposition with a laminar flow in a float bath onto a moving float glass ribbon in a glass manufacturing process. In these Examples, a double layer coating was applied to a glass tape.

All gas volumes are measured at normal temperature and pressure, unless otherwise specified. The thicknesses indicated for the layers were determined using a high resolution scanning electron microscope and optical modeling of reflection and transmission spectra of coated glass. The thickness of the coatings was measured with an error of about 5%. The transmission and reflection properties of coated glasses were determined using a NYASA-4000 spectrophotometer. The values ​​of a, b, and b * referred to here with respect to the transmission and / or reflection of glasses were evaluated using the C1E bab system. Reflection and transmission of visible light for coated glasses was determined using a Ώ65 light source and a standard C1E 2 ° meter, in accordance with standard 180 9050 (Raggu Moop IT 2). The haze coefficients of coated glasses were measured using \ UK-Sagdpeg Nagadiages! + nephelometer.

The photocatapitic activity of coated glasses was determined by the degree of decrease in the area of ​​infrared peaks corresponding to the CH lines of the stearic acid film on the coated surface of the glass under irradiation with ultraviolet A. The stearic acid film was deposited on η

glass samples with an area of ​​7-8 cm by centrifugation of 20 μl of a solution of stearic acid in methanol (8.8 x 10 '³ mol dm¹) on a coated glass surface at 2000 rpm. within 1 min. Infrared spectra were measured with transmission; measured the height of the peak corresponding to the CH lines (at about 2700-3000 cm¹) films of stearic acid, and the corresponding peak area was determined from the calibration curve of the dependence of the peak area on the height of the peak. The coated side of the glass was illuminated with a UVA-351 lamp (purchased from () -Paep1 Co., C1eue1apb, Oyo, ΙΙ8Α), which has a peak wavelength of 351 nm and an intensity near the surface of the coated glass of about 32 W / m. Photocatalytic activity in this description is expressed either as the rate of decrease in the area of ​​IR peaks (in cm '¹min. '¹) or like ί₉ο% (in min.), which is the UV irradiation time necessary to reduce the peak height (absorption) in the region of a given wavelength to 10% of its initial value.

The contact angle with water for coated glasses was determined by measuring the diameter of a drop of water (from 1 to 5 μl) placed on the surface of the coated glass after irradiating the coated glass with a UVA-351 lamp for about 2 hours (or as indicated in Example )

Examples 1-15

On a tape of sodium-calcium-silicate glass with a thickness of 1 mm, with a speed of 300 m / h in the lehr, a two-layer coating was applied when the tape passed through the float bath in the place where the glass temperature was in the range from ~ 650 ° С to ~ 670 ° C. The atmosphere of the float bath consisted of a gaseous mixture of nitrogen and 9% hydrogen at a pressure in the bath of about 0.15 mbar.

Layer 1 (the first layer deposited on glass) was a layer of silicon oxide. Layer 1 was precipitated by contact of glass with a gaseous mixture of monosilane (8ΐΗ₄, 60 ml / min.), Oxygen (120 ml / min.), Ethylene (360 ml / min.), And nitrogen (8 l / min.), The flow of which was moved parallel to the glass surface in the direction of glass movement, using the apparatus for coating, as described in patent OV 1 507 966 (in particular, in Fig. 2 and in the description thereto on page 3, line 73 - page 4, line 75), while the length of the path of the gaseous mixture along the glass surface was about 0.15 m. The extraction was carried out at a pressure of about 0.9-1.2 mbar. The coating on the glass tape was applied at a width of about 10 cm at the point where the temperature of the tape was ~ 670 ° C. The silica layer had a thickness of about 20-25 nm.

Layer 2 (second deposited layer) was a titanium dioxide layer. Layer 2 was precipitated by combining separate gas streams containing titanium tetrachloride in a gaseous nitrogen carrier, ethyl acetate in a gaseous nitrogen carrier and a transporting nitrogen stream with a flow rate of 8 l / min. (flow rate was measured at a pressure of 20 psi inch (~ 1.4 bar)) into the gaseous mixture, which was then fed (via supply pipelines, the temperature of which was maintained at ~ 250 ° C) to a coating plant, including a two-line oil-cooled coating machine. The pressure of the carrier nitrogen and carrier nitrogen was about 20 psi. inch (~ 1.4 bar).

The gaseous mixture was in contact with the surface of the glass, flowing parallel to it in the direction and towards the direction of movement of the glass ribbon. The length of the path of the gaseous mixture in the direction of flow was about 0.15 m, towards the direction of flow - 0.15 m, extraction was carried out at a pressure of about 0.15 mbar. Titanium tetrachloride and ethyl acetate were introduced into separate nitrogen carrier streams by passing nitrogen through bubblers containing titanium tetrachloride or ethyl acetate. The flow rates of gas carriers are given in Table. 1 (measured at 20 psi (~ 1.4 bar)). The bubbler for titanium tetrachloride had a temperature of 69 ° C, and the bubbler for ethyl acetate had a temperature of 42 ° C. The calculated rates of titanium tetrachloride involved in the process and ethyl acetate involved in the process are also given in Table. 1 for each of Examples 1-15.

Then evaluated the properties of two-layer coatings. The thickness of layer 2 (titanium oxide layer) and the reflection of visible light, measured on the coated side, b * and the haze coefficients of coated glasses are given in Table. 2 for Examples 1-15. The haze coefficient of each of the coated glasses was below 0.2%.

The photocatalytic activity and the contact angle with water were also determined for coated glasses. The initial peak height and the initial peak area for IR peaks corresponding to the CH sites of stearic acid, photocatalytic activity, contact angle with water and ί₉οο /₀ for Examples 1-15 are shown in Table. 3. Unexpectedly, the thickness of the titanium oxide layer does not significantly affect the photocatalytic activity.

Examples 16-19

Examples 16-19 were performed under the same conditions as Examples 1-15, except that the pressure in the bath was about 0.11 mbar, extraction during the deposition of a silica underlying layer (layer 1) was carried out at a pressure of about 0.7 mbar , the bubbler for titanium tetrachloride was maintained at a temperature of about 100 ° C, the bubbler for ethyl acetate was maintained at a temperature of about 45 ° C, and the supply lines were maintained at a temperature of about 220 ° C.

The carrier nitrogen rates and the estimated rates of the titanium tetrachloride involved and the ethyl acetate involved are shown for each of Examples 16-19 in Table. one.

The calculated thicknesses of layer 2 (titanium oxide layer) and the reflection of visible light, measured on the coated side b * and the haze coefficients of coated glasses are given in Table. 2 for Examples 16-19.

The initial peak height and the initial peak area for IR peaks corresponding to CH lines of stearic acid, photocatalytic activity, ί₉₀% and the contact angle with water for each of Examples 1619 are shown in Table. 3.

The photocatalytic activity in Examples 16-19 was not significantly higher than in Examples 1-15, despite the thicker (and therefore having a higher reflectivity) titanium oxide coatings.

Table 1

<td>Example</td><td colspan="2">Nitrogen carrier gas flow rates through bubblers (l / min., Measured at 20 psi (1.4 bar))</td><td rowspan="2">Speed ​​'PS1₄(l / min.)</td><td rowspan="2">Speed currents ethyl acetate (l / min.)</td>

<td></td><td>Bubbler TU1₄</td><td>Bubbler ethyl acetate</td>

<td> 1</td><td> 0,16</td><td> 1</td><td> 0,032</td><td> 0,46</td>

<td> 2</td><td> 0,12</td><td> 0,3</td><td> 0,024</td><td> 0,14</td>

<td> 3</td><td> 0,12</td><td> 0,45</td><td> 0,024</td><td> 0,21</td>

<td> 4</td><td> 0,08</td><td> 0,2</td><td> 0,016</td><td> 0,09</td>

<td> 5</td><td> 0,12</td><td> 0,15</td><td> 0,024</td><td> 0,07</td>

<td> 6</td><td> 0,12</td><td> 0,75</td><td> 0,024</td><td> 0,35</td>

<td> 7</td><td> 0,08</td><td> 0,3</td><td> 0,016</td><td> 0,14</td>

<td> 8</td><td> 0,08</td><td> 0,5</td><td> 0,016</td><td> 0,23</td>

<td> 9</td><td> 0,04</td><td> 0,1</td><td> 0,008</td><td> 0,05</td>

<td> 10</td><td> 0,04</td><td> 0,15</td><td> 0,008</td><td> 0,07</td>

<td> 11</td><td> 0,04</td><td> 0,25</td><td> 0,008</td><td> 0,12</td>

<td> 12</td><td> 0,16</td><td> 0,1</td><td> 0,032</td><td> 0,05</td>

<td> 13</td><td> 0,08</td><td> 0,1</td><td> 0,016</td><td> 0,05</td>

<td> 14</td><td> 0,16</td><td> 0,4</td><td> 0,032</td><td> 0,19</td>

<td> 15</td><td> 0,16</td><td> 0,2</td><td> 0,032</td><td> 0,09</td>

<td> 16</td><td> 0,1</td><td> 0,5</td><td> 0,088</td><td> 0,27</td>

<td> 17</td><td> 0,08</td><td> 0,4</td><td> 0,070</td><td> 0,22</td>

<td> 18</td><td> 0,06</td><td> 0,3</td><td> 0,053</td><td> 0,16</td>

<td> 19</td><td> 0,04</td><td> 0,2</td><td> 0,035</td><td> 0,11</td>

table 2

<td>Example</td><td>The thickness of the titanium oxide layer (nm)</td><td>Reflection of visible light for coated glass (%)</td><td>The value of b * for glass with coating (%)</td><td>Dull (%)</td>

<td> 1</td><td> 15</td><td> 14,1</td><td> 44</td><td> 0,12</td>

<td> 2</td><td> 14,3</td><td> 13,9</td><td> 44</td><td> 0,07</td>

<td> 3</td><td> 14,2</td><td> 13,2</td><td> 43</td><td> 0,12</td>

<td> 4</td><td> 11,3</td><td>P, 4</td><td> 40</td><td> 0,08</td>

<td> 5</td><td> 12,1</td><td> 12,1</td><td> 41</td><td> 0,08</td>

<td> 6</td><td> 11,0</td><td>BUT</td><td>but</td><td> 0,07</td>

<td> 7</td><td> 8</td><td>BUT</td><td>but</td><td> 0,11</td>

<td> 8</td><td> 7,2</td><td> 9,7</td><td> 37</td><td> 0,04</td>

<td> 9</td><td> 6,1</td><td> 9,1</td><td> 36</td><td> 0,05</td>

<td> 10</td><td> 5,6</td><td> 9</td><td> 36</td><td> 0,07</td>

<td> 11</td><td> 4,6</td><td> 8,7</td><td> 35</td><td> 0,06</td>

<td> 12</td><td> 15,6</td><td> 15,4</td><td> 46</td><td> 0,1</td>

<td> 13</td><td> 16,0</td><td>BUT</td><td>but</td><td> 0,13</td>

<td> 14</td><td> 17,5</td><td> 16,2</td><td> 47</td><td> 0,14</td>

<td> 15</td><td> 20,3</td><td> 19,5</td><td> 51</td><td> 0,1</td>

<td> 16</td><td>but</td><td> 28,4</td><td> 47,8</td><td> 0,3</td>

<td> 17</td><td> ~68</td><td> 29,1</td><td> 58,4</td><td> 0,37</td>

<td> 18</td><td> ~32</td><td> 25,9</td><td> 55,6</td><td> 0,24</td>

<td> 19</td><td> ~27</td><td> 20,5</td><td> 50,2</td><td> 0,2</td>

a - not measured

Table 3

<td rowspan="2">Example</td><td colspan="2">IR peaks corresponding to the CH sections of the stearic acid film (27003000 cm '¹)</td><td rowspan="2">Photocatal ethical activity (χ 10 '² cm'¹min. '¹)</td><td rowspan="2">Static angle contact with water (°)</td><td rowspan="2">* 90% (min)</td>

<td>Original peak height (conditional units)</td><td>Original peak area (cm '¹)</td>

<td> 1</td><td> 0.030</td><td> 1.04</td><td> 9.4</td><td> 17±5</td><td> 10</td>

<td> 2</td><td> 0.0331</td><td> 1.15</td><td> 10.4</td><td> 15 ±1</td><td> 10</td>

<td> 3</td><td> 0.0311</td><td> 1.08</td><td> 12.2</td><td> 13±2</td><td> 8</td>

<td> 4</td><td> 0.0324</td><td> 1.13</td><td> 6.8</td><td> 14 ±1</td><td> 15</td>

<td> 5</td><td> 0.0287</td><td> 1.00</td><td> 8,2</td><td> 16±3</td><td> 11</td>

<td> 6</td><td> 0.028</td><td> 0.98</td><td> 8.8</td><td> 15 ±1</td><td> 10</td>

<td> 7</td><td> 0.0343</td><td> 1.20</td><td> 10.8</td><td> 15 ±1</td><td> 10</td>

<td> 8</td><td> 0.0289</td><td> 1.03</td><td> 6.6</td><td> 16 ±1</td><td> 14</td>

<td> 9</td><td> 0.0289</td><td> 1.01</td><td> 6,5</td><td> 14 ±2</td><td> 14</td>

<td> 10</td><td> 0.0278</td><td> 0.97</td><td> 6.2</td><td> 18±2</td><td> 14</td>

<td> 11</td><td> 0.0344</td><td> 1.20</td><td> 5,4</td><td> 18 ±1</td><td> 20</td>

<td> 12</td><td> 0,0291</td><td> 1.02</td><td> 10,2</td><td> 12 ±1</td><td> 9</td>

<td> 13</td><td> 0.0289</td><td> 1.01</td><td> 9,1</td><td> 14 ±2</td><td> 10</td>

<td> 14</td><td> 0.0269</td><td> 0.94</td><td> 9.4</td><td> 15±2</td><td> 9</td>

<td> 15</td><td> 0.0331</td><td> 1.15</td><td> 8.7</td><td> 15±2</td><td> 12</td>

<td> 16</td><td> 0.0227</td><td> 0.79</td><td> 17.8</td><td> 12</td><td> 4</td>

<td> 17</td><td> 0.026</td><td> 0.91</td><td> 10.2</td><td> 12</td><td> 8</td>

<td> 18</td><td> 0.0225</td><td> 0.79</td><td> 10.1</td><td> 13</td><td> 7</td>

<td> 19</td><td> 0,0258</td><td> 0,90</td><td> 10,1</td><td> 16</td><td> 8</td>

Examples 20-27

Examples 20-27 were performed under the same conditions as Examples 1-15, with the exception that layer 2 was deposited from a gaseous mixture containing titanium tetraethoxide involved in a nitrogen gas carrier by passing the carrier gas through a bubbler containing titanium tetraethoxide at a temperature of 170 ° C. The flow rates of the nitrogen carrier (measured at 20 psi) and titanium tetraethoxide are shown in Table. 4 for each of Examples 20-27. The volumetric nitrogen flow rate was 8.5 L / min. (measured at 20 psi (1.4 bar)).

The properties of two-layer coatings were evaluated. The thicknesses of layer 2 (titanium oxide layer) and the reflection of visible light, measured on the coated side, as well as the haze coefficients of coated glasses are given in Table. 5 for Examples 20-27. The haze coefficient of each of the coated glasses was below 0.7%.

The photocatalytic activity and the contact angle with water were determined for coated glasses. The initial peak height and the original peak area for IR peaks corresponding to the CH sites of stearic acid, photocatalytic activity, 1₉₀»/_about and the contact angle with water for each of Examples 20-27 are shown in Table. 6.

Examples 28 and 29

Examples 28 and 29 were performed under the same conditions as Examples 20-27, with the exception that the bubbler for titanium tetraethoxide was maintained at a temperature of 168 ° C and the pressure in the bath was 0.11 mbar. The data for Examples 28-29, equivalent to the data for Examples 20-27, are shown in Table. 4, 5 and 6.

Table 4

<td>Example</td><td>Nitrogen carrier gas flow rates into the bubbler of titanium tetraethoxide (l / min., Measured at 20 psi (1.4 bar))</td><td>The flow rate of titanium tetraethoxide (l / min.)</td>

<td> 20</td><td> 0.25</td><td> 0,014</td>

<td> 21</td><td> 0.15</td><td> 0,008</td>

<td> 22</td><td> 0.2</td><td> 0.011</td>

<td> 23</td><td> 0.25</td><td> 0.014</td>

<td> 24</td><td> 0.3</td><td> 0.017</td>

<td> 25</td><td> 0.35</td><td> 0.019</td>

<td> 26</td><td> 0.2</td><td> 0.011</td>

<td> 27</td><td> 0.1</td><td> 0.006</td>

<td> 28</td><td> 0.6</td><td> 0.030</td>

<td> 29</td><td>Ol</td><td> 0,020</td>

Table 5

<td>Example</td><td>Thickness titanium oxide layer (nm)</td><td>Reflection of visible light for glass with dripping</td><td>Haze (%)</td>

<td> 20</td><td> 13</td><td>but</td><td> 0.4</td>

<td> 21</td><td> 13</td><td>but</td><td> 0.29</td>

<td> 22</td><td> 16</td><td> 15.7</td><td> 0.29</td>

<td> 23</td><td> 18</td><td>but</td><td> 0,28</td>

<td> 24</td><td> 24</td><td>but</td><td>but</td>

<td> 25</td><td> 26</td><td>but</td><td> 0.61</td>

<td> 26</td><td> 9.9</td><td> 10.9</td><td> 0.19</td>

<td> 27</td><td> 4.7</td><td> 8.8</td><td> 0.29</td>

<td> 28</td><td> 38.3</td><td> 35.2</td><td> 0,29</td>

<td> 29</td><td> 31,9</td><td> 28,4</td><td> 0,22</td>

a - not measured

Table 6

<td rowspan="2">Example</td><td colspan="2">IR peaks, corresponding to CH sections of the stearic acid film (2700-3000 cm¹)</td><td rowspan="2">Photocataly cheskaya activity (x 10 '² cm'¹ min. '¹)</td><td rowspan="2">Static contact angle with water (°)</td><td rowspan="2">Ϊ90% (min)</td>

<td>Original peak height (conditional units)</td><td>Original peak area (cm '¹)</td>

<td> 20</td><td> 0,027</td><td> 0,953</td><td> 5,7</td><td> 19±5</td><td> 15</td>

<td> 21</td><td> 0,031</td><td> 1,095</td><td> 5,7</td><td>but</td><td> 17</td>

<td> 22</td><td> 0,024</td><td> 0,838</td><td> 3,6</td><td> 15±2</td><td> 21</td>

<td> 23</td><td> 0,030</td><td> 1,029</td><td>7D</td><td> 11±3</td><td> 13</td>

<td> 24</td><td> 0,029</td><td> 1,015</td><td> 7</td><td> 17±3</td><td> 13</td>

<td> 25</td><td> 0,031</td><td> 1,071</td><td> 7,4</td><td> 13±4</td><td> 13</td>

<td> 26</td><td> 0,031</td><td> 1,085</td><td> 4,4</td><td> 21±3</td><td> 22</td>

<td> 27</td><td> 0,029</td><td> 0,998</td><td> 3,2</td><td> 16±5</td><td> 28</td>

<td> 28</td><td> 0,021</td><td> 0,733</td><td> 3,6</td><td> 13</td><td> 18</td>

<td> 29</td><td> 0,024</td><td> 0,848</td><td> 3,3</td><td> 14</td><td> 23</td>

a - not measured

Examples 30-42

In Examples 30-42, two-layer coatings were applied on-line using the SUL method on a float glass ribbon over its entire width of about 132 inches (3.35 m) in a float bath during the production of float glass. The apparatus used for coating deposition is shown in FIG. 2. The atmosphere in the float bath consisted of nitrogen and 2% (vol.) Hydrogen. The pressure in the bath was 0.15 mbar.

The two-layer coating consisted of a silicon oxide layer deposited first on a float glass ribbon and a titanium oxide layer deposited on a silicon oxide layer. The technologies for preparing the initial gas mixtures used for coating deposition were the same as in Examples 1-15. The deposition temperature of the layers was varied by using various coating devices 27, 28, 29 or 30 (see FIG. 2). Coating device 27, the closest to the furnace, was the hottest, and device 30, closest to the lehr, was the coldest. In Examples 30-33 and 42, two coating devices (28 and 29 in Examples 30-33 and devices 27 and 28 in Example 42) were used to deposit a layer of silicon oxide. An advantage of using two coating devices to deposit a silica layer is that longer production periods are possible.

The gaseous mixture for the deposition of a layer of silicon oxide in Examples 30-41 consisted of the following gases with the following flow rates: helium (250 l / min.), Nitrogen (285 l / min.), Monosilane (2.5 l / min.) ethylene (15 l / min.) and oxygen (10 l / min.). In Example 42, the same gases and velocities were used except for the velocities of monosilane (2.3 L / min.), Ethylene (13.8 L / min.) And oxygen (9.2 L / min.). In those cases where two coating devices were used to deposit a silica layer in Examples 30-42, the indicated flow rates were used for each of the devices.

In Examples 30-42, the deposition temperatures (i.e., the temperatures of the float glass tape under the coating devices corresponding to each of the devices 27-30) were as indicated in Table. 7. Temperatures in Tab. 7 have an error of about ± 50 ° P (± 28 ° C). Extraction from each of the coating plants was carried out at approximately 2 mbar.

Table 7

<td>Coating Device</td><td>Estimated tape temperature glass</td>

<td> 27</td><td>1330 ° P (721 ° C)</td>

<td> 28</td><td>1275 ° P (690 ° C)</td>

<td> 29</td><td>1250 ° P (677 ° C)</td>

<td> 30</td><td>1150 ° P (621 ° C)</td>

Titanium Tetrachloride (SPSC) and ethyl acetate were drawn into separate streams of a carrier gas (nitrogen / helium). For evaporation of T1C1₄ used a thin film evaporator. Liquid T1O4 was in a pressurized container (outlet pressure about 5 psi (0.35 bar)). Pressure was used to supply fluid to the metering pump and the Coriolis flow rate measuring system. The dosed primary gas stream was then fed to a thin film evaporator at a temperature of 110 ° P (43 ° C). Then ΤίΟ1₄ introduced into the carrier gas (helium) and fed into the downstream pipelines leading to the mixing point, the temperature of which was maintained equal at 250 ° P (121 ° C). Ethyl acetate was introduced in the same manner. Liquid ethyl acetate was pressurized in an airtight container (outlet pressure about 5 psi), from where it was fed to a metering pump and a Coriolis flow rate measuring system. The dosed primary gas stream was then fed into a thin film evaporator at a temperature of 268 ° P (131 ° C). Then, the evaporated ethyl acetate was introduced into the carrier gas (helium / nitrogen mixture) and fed into the descending pipelines leading to the mixing point at the temperature of the latter 250 ° P (121 ° C).

The gas jets of TJC and ethyl acetate were combined to form a gaseous mixture used to precipitate a titanium oxide layer. This mixing point was directly in front of the coating device.

The linear velocity of the float glass ribbon, the deposition temperature of the silicon oxide layer and the deposition temperature of the titanium oxide layer, as well as the volumetric flow rates of the carrier gas Ηε / Ν₂ and current velocity ΤίΟ1₄ and ethyl acetate are given for Examples 30-42 in Table. 8.

The coated float glass ribbon was cooled, cut, and the optical properties and photocatalytic activity of the samples were determined. In Tab. Figure 9 shows the haze coefficients and optical properties (percent transmittance / reflection of visible light and color coordinates according to the C1E 1ab system) of the samples. Coated glasses were tested for abrasion in accordance with the procedure ВЗ ΕΝ 1096, in which a 300 mm x 300 mm specimen was rigidly fixed at four angles on the test bench so as to ensure its immobility. A fresh felt pad is cut to the dimensions specified in the standard (B3 1096 Pag1 2 (1999)), attached to the test pin and the pin is lowered onto the glass surface. Then set the load pressure on the test pin 4 N and begin the test. The pin makes 500 reciprocating moves along the surface of the sample at a speed of 60 strokes / min. ± 6 strokes / min. At the end of the test, the sample is removed and examined optically and for photocatalytic activity. A sample is considered to have passed the test if attrition led to a transmission change of not more than 5% (measurement at 550 nm) and the coated substrate retained photocatalytic activity, i.e., after testing, irradiation with ultraviolet light for 2 hours reduces the contact angle with water to below 15 °.

Glasses were also subjected to cyclic moisture resistance tests, in which the coating was subjected to a temperature cycle of 35 ° C-75 ° C-35 ° C for 4 hours at almost 100% relative humidity.

The contact angle with water for coated glasses after manufacture, after 130 minutes of UV irradiation (UVA lamp with a wavelength of 351 nm and an intensity of about 32 W / m²) and after 300, 500 and / or 1000 moves in the abrasion test according to the European standard are given in Table. 10. The contact angle of the abraded samples was determined after irradiation for 2 hours.

Samples deposited at higher temperatures of 1330-1250 ° P (721677 ° C) retained photocatalytic activity even after 1000 strokes in the abrasion test according to the European standard or after 200 cycles of moisture resistance test. Photocatalytic activity values ​​as ΐ₉₀% for coated glass after manufacturing, after 300, 500 and / or 1000 strokes in the abrasion test according to the European standard and after 200 cycles of moisture resistance tests are given in Table. 11. In Tab. 11 marked active means that coated glass was photocatalytically active, but Ϊ9ο% was not determined.

Table 8

<td>Example</td><td>Linear speed (m / min.)</td><td rowspan="2">Silica deposition temperature (° C)</td><td colspan="5">Titanium oxide layer</td>

<td></td><td></td><td>Temperature precipitation</td><td colspan="2">Gas carrier flow rates</td><td>Speeds flowing) κοιν</td><td>chiya preliminary components</td>

<td></td><td></td><td></td><td></td><td>Not l / min</td><td>Ν₂ l / min</td><td>T1S14 cm³/ min</td><td>Ethyl acetate cm³/ min</td>

<td> 30</td><td> 10,9</td><td>690 and 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6,3</td><td> 16,3</td>

<td> 31</td><td> 10.9</td><td>690 and 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6.3</td><td> 16,3</td>

<td> 32</td><td> 10.9</td><td>690 and 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6.3</td><td> 16,3</td>

<td> 23</td><td> 10.9</td><td>690 and 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6.3</td><td> 16.3</td>

<td> 34</td><td> 10.9</td><td> 690</td><td> 621</td><td> 300</td><td> 300</td><td> 6</td><td> 16</td>

<td> 35</td><td> 10.9</td><td> 690</td><td> 621</td><td> 300</td><td> 300</td><td> 6</td><td> 16</td>

<td> 36</td><td> 10.9</td><td> 690</td><td> 621</td><td> 300</td><td> 300</td><td> 6</td><td> 16</td>

<td> 37</td><td> 10,9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5.5</td><td> 14.7</td>

<td> 38</td><td> 10.9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5.5</td><td> 14.7</td>

<td> 39</td><td> 10.9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5.5</td><td> 14.7</td>

<td> 40</td><td> 10.9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5.5</td><td> 14.7</td>

<td> 41</td><td> 6,5</td><td> 721</td><td> 690</td><td> 300</td><td> 300</td><td> 4</td><td> 10,7</td>

<td> 42</td><td>12D</td><td>721 and 690</td><td> 677</td><td> 300</td><td> 300</td><td> 9,5</td><td> 25,4</td>

Table 9

<td rowspan="2">Example</td><td colspan="4">Film reflection</td><td colspan="4">Skipping</td><td rowspan="2">Haze (%)</td>

<td>K ί%)</td><td>B *</td><td>but</td><td>b</td><td>T g%)</td><td>B *</td><td>but</td><td>B</td>

<td> 30</td><td> 14.2</td><td> 44.5</td><td> 0.3</td><td> -10.3</td><td> 84.3</td><td> 93,6</td><td> -1.2</td><td> 3.6</td><td> 0,11</td>

<td> 31</td><td> 14,6</td><td> 45,1</td><td> 0,3</td><td> -10.4</td><td> 84.5</td><td> 93.7</td><td> ,1,1</td><td> 3.4</td><td> 0,30</td>

<td> 32</td><td> 14.6</td><td> 45.1</td><td> 0.3</td><td> -10.5</td><td> 84.3</td><td> 93.6</td><td> -1,1</td><td> 3.6</td><td> 0.12</td>

<td> 33</td><td> 13.8</td><td> 44.0</td><td> 0.3</td><td> -9,8</td><td> 85.5</td><td> 94.1</td><td> -1.1</td><td> 2.9</td><td> 0.15</td>

<td> 34</td><td> 13,6</td><td> 43.7</td><td> 0,1</td><td> -8,7</td><td> 84.8</td><td> 93.8</td><td> -1,1</td><td> 2,7</td><td> 0,12</td>

<td> 35</td><td> 13.8</td><td> 43.9</td><td> 0,1</td><td> -8.8</td><td> 85.4</td><td> 94.1</td><td> -1.1</td><td> 2.6</td><td> 0.11</td>

<td> 36</td><td> 12.9</td><td> 42,6</td><td> 0,1</td><td> -8.2</td><td> 85.8</td><td> 94.2</td><td> -1.1</td><td> 2,5</td><td> 0.14</td>

<td> 37</td><td> 12,6</td><td> 42.2</td><td> 0,1</td><td> -7.9</td><td> 86.1</td><td> 94.4</td><td> -1,1</td><td> 2,3</td><td> 0,08</td>

<td> 38</td><td> 11,9</td><td> 41.0</td><td> 0,1</td><td> -6,9</td><td> 87.1</td><td> 94.8</td><td> -1.1</td><td> 1.7</td><td> 0,07</td>

<td> 39</td><td> 11,5</td><td> 40,4</td><td> 0,0</td><td> -6,5</td><td> 87,2</td><td> 94,8</td><td> -1,1</td><td> 1,8</td><td> 0,10</td>

<td> 40</td><td> 11.6</td><td> 40.6</td><td> 0.0</td><td> -6,6</td><td> 86.9</td><td> 94.7</td><td> -1,1</td><td> 1,8</td><td> 0.08</td>

<td> 41</td><td>but</td><td>but</td><td>but</td><td>but</td><td>but</td><td>but</td><td>but</td><td>but</td><td>but</td>

<td> 42</td><td> 14</td><td> 44,3</td><td> 0,1</td><td> -9,9</td><td> 84,8</td><td> 93,8</td><td> -1,1</td><td> 3,1</td><td> 0,14</td>

a - not measured

Table 10

<td rowspan="2">Example</td><td colspan="5">Static contact angle with water (°) after the following number of abrasive strokes:</td>

<td> 0</td><td>0 (after 130 min. UV irradiation)</td><td> 300</td><td> 500</td><td> 1000</td>

<td> 30</td><td> 2,3</td><td> 3,3</td><td>renouncement</td><td></td><td></td>

<td> 31</td><td> 2,0</td><td> 3,2</td><td>renouncement</td><td></td><td></td>

<td> 32</td><td>but</td><td>but</td><td>renouncement</td><td></td><td></td>

<td> 33</td><td> 2,0</td><td> 3,2</td><td>renouncement</td><td></td><td></td>

<td> 34</td><td>but</td><td>but</td><td>renouncement</td><td></td><td></td>

<td> 35</td><td> 2,0</td><td> 3,2</td><td>renouncement</td><td></td><td></td>

<td> 36</td><td> 2,1</td><td> 3,4</td><td>renouncement</td><td></td><td></td>

<td> 37</td><td> 2,2</td><td> 3,3</td><td></td><td> &lt;15</td><td></td>

<td> 38</td><td> 2,0</td><td> 3,1</td><td></td><td> &lt;15</td><td></td>

<td> 39</td><td> 1,9</td><td> 3,1</td><td></td><td> &lt;15</td><td></td>

<td> 40</td><td> 2,2</td><td> 3,2</td><td></td><td> &lt;15</td><td></td>

<td> 41</td><td> 7,8</td><td> 7,8</td><td></td><td></td><td> 10,1</td>

<td> 42</td><td> 4,7-5,3</td><td> 4,7-5,3</td><td></td><td></td><td> 5,6-9,8</td>

a - not measured

Table 11

<td rowspan="2">Example</td><td colspan="4">ΐ₉₀% (min.) after the following number of abrasive moves:</td><td rowspan="2">ί₉ο% (min.) after 200 test cycles on moisture resistance</td>

<td> 0</td><td> 300</td><td> 500</td><td> 1000</td>

<td> 30</td><td> 7,5</td><td>renouncement</td><td></td><td></td><td>Renouncement</td>

<td> 31</td><td> 18,5</td><td>renouncement</td><td></td><td></td><td>Renouncement</td>

<td> 32</td><td> 8,5</td><td>renouncement</td><td></td><td></td><td>Renouncement</td>

<td> 33</td><td> 8</td><td>renouncement</td><td></td><td></td><td>Renouncement</td>

<td> 34</td><td> 21</td><td>renouncement</td><td></td><td></td><td>Renouncement</td>

<td> 35</td><td> 4</td><td>renouncement</td><td></td><td></td><td>Renouncement</td>

<td> 36</td><td> 8,5</td><td>renouncement</td><td></td><td></td><td>Renouncement</td>

<td> 37</td><td> 15,5</td><td></td><td> -2160</td><td></td><td>active</td>

<td> 38</td><td> 18,5</td><td></td><td> -2160</td><td></td><td>active</td>

<td> 39</td><td> 17</td><td></td><td> -2160</td><td></td><td>active</td>

<td> 40</td><td> 18,5</td><td></td><td> -2160</td><td></td><td>active</td>

<td> 41</td><td>but</td><td></td><td></td><td> -2160</td><td>active</td>

<td> 42</td><td> 45</td><td></td><td></td><td> 2800</td><td>active</td>

a - not measured