Photocatalytically active coated substrates

The first method of producing a photocatalytic coating on a substrate. The patent application of the present invention is a subdivision of the invention patent application with the application date of June 1, 2000, application number 00808643.5, and the title of the invention: "Method for Producing Photocatalytic Coating on a Substrate" Case application.

The present invention relates to a production of photocatalytically active coated substrates, particularly but not exclusively, it relates to a method of producing photocatalytically active coated glass and this coated glass.

It is known to deposit one or more layers of coatings with various properties on substrates (including on glass substrates). A meaningful performance is photocatalytic activity. When a semiconductor is irradiated with light of a specific frequency, the photocatalytic activity is generated by the hole-electron pair generated by the light in the semiconductor. Hole-electron pairs can be generated in sunlight and can react in humid air to form amino groups and peroxide groups on the surface of the semiconductor. These groups oxidize organic dirt on the surface. This performance has applications in self-cleaning substrates (especially self-cleaning window glass).

Titanium dioxide can be an effective photocatalyst and can be deposited on the substrate to form a transparent coating with photocatalytic self-cleaning properties. In EP 0 901 991 A2, W097/07069. W0 97/10186, W098/41480. Abstract 735 of the 187th Meeting of the Electrochemical Society (Reno, NV, 95-1, p. 1102) and the Journal of New Scientist (1995) On August 26, p19), a titanium oxide photocatalytic coating was disclosed. In WO 98/06675, a chemical vapor deposition method is described for depositing a titanium oxide coating on a hot flat glass at a high deposition rate, in which a precursor gas mixture of titanium chloride and an organic compound as an oxygen source is used To form a titanium oxide coating.

It has been considered that in order to provide good photocatalytic activity, a relatively thick titanium oxide film needs to be deposited. For example, in WO 98/41480, it is stated that the photocatalytic active self-cleaning coating must be thick enough to provide a qualified level of activity. Preferably, the coating is at least about 200 angstroms thick, and more preferably at least about 500 angstroms. Thick (the measured thickness of the titanium oxide coating produced in the examples is in the range of 400-2100 angstroms).

However, the problem with the thicker titanium oxide coating is that the visible light reflectance is high, and therefore the visible light transmittance is low. This issue is considered in the article on coated windshield in the New Scientist Magazine. In this article, it is proposed that in order to reduce the impact of high reflection, the instrument panel must be covered with black velvet or other light that does not reflect light to the coated windshield. material.

The EP 0 901 991A2 mentioned above relates to a titanium oxide coating with a specific crystal structure

200810002407.2 No. Photocatalytic window glass, the coating is characterized by the presence of specific peaks in its X-ray diffraction spectrum. The thickness range of the coating should be considered (the thickness of all specific examples is between 20 nm and 135 nm, and the photocatalytic activity of thinner coatings is lower than that of thicker coatings). This also considers that the deposition temperature ranges from as low as 300°C to as high as 750°C, but the preferred temperature is between 400°C and 600°C. In all the specific embodiments of the present invention, within the preferred range or lower The titanium dioxide film is deposited in this preferred temperature range.

The inventors have now discovered that by depositing a titanium oxide coating at a higher temperature, especially above 600°C, for a certain thickness, a coating with enhanced photocatalytic activity can be obtained, and a thinner coating can be used. Obtain the same photocatalytic performance. This thinner coating is advantageous in that it tends to have lower visible light reflectivity and, apparently, due to its higher deposition temperature, it has improved durability, especially for abrasion and temperature cycling in humid gases.

Therefore, the present invention provides a method for producing a photocatalytically active coated substrate, which includes depositing a titanium oxide coating on the surface of the substrate by contacting the surface of the substrate with a fluid mixture containing a titanium source and an oxygen source, and the temperature of the substrate is at least 600 °C, so that the coating surface of the substrate has a size greater than SxlO^cm^min ¹The photocatalytic activity, the visible light reflectance measured on the coating side is 35% or less.

Preferably, the temperature of the substrate is in the range of 625 to 720°C, and more preferably, the temperature of the substrate is in the range of 645 to 720°C.

Advantageously, the fluid mixture contains titanium chloride as a source of titanium and esters that are not methyl esters. Therefore, in a preferred embodiment, the present invention provides a method for producing a photocatalytically active coated substrate, which includes contacting the surface of the substrate with a fluid mixture containing titanium chloride and an ester other than methyl ester, and A titanium oxide coating with a thickness of less than 40 nanometers is deposited.

Wherein, when the substrate temperature is in the range of 600-750°C, the surface of the substrate is brought into contact with the fluid mixture to perform the method.

Preferably, the ester is an alkyl ester with an alkyl group with hydrogen (the alkyl group of the alkyl ester is a group derived from an alcohol during the synthesis of the ester, and the hydrogen is bound to the ester relative to the The oxygen in the squint bond is the hydrogen on the carbon atom at the J position). Preferably, the ester is a carboxylate.

Suitable esters can be C₂ -c₁₀Alkyl esters of alkyl groups, however, it is preferred that the esters are alkyl esters having C2-C4 alkyl groups.

200810002407.2 The first preferred is that the ester is a compound of the formula: RC(0)-OC(X)(X,)-C(Y)(Y,)-R, wherein R and R represent hydrogen or The alkyl group, X, X, Y, and Y, represent a monovalent substituent, preferably an alkyl group or a hydrogen atom, wherein at least one of Y and Y represents a hydrogen atom.

Suitable esters that can be used in the method of the present invention include: ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, n-propyl formate, n-propyl acetate, n-propyl propionate, n-butyrate Propyl ester, isopropyl formate, isopropyl acetate, isopropyl propionate, isopropyl butyrate, n-butyl formate, n-butyl acetate, and tert-butyl acetate.

Preferably, the ester contains an ethyl ester, and more preferably, the ester contains ethyl formate, ethyl acetate, or ethyl propionate. It is most preferred that the ester contains ethyl acetate.

The fluid mixture may be in liquid form, especially dispersed into fine mist droplets (a method commonly referred to as spray deposition), but it is preferred that the fluid mixture is a gas mixture. The deposition method using a gas mixture as a precursor is often referred to as chemical vapor deposition (CVD), and the preferred form of CVD is laminar flow CVD, although turbulent flow CVD can also be used.

The method can be performed on substrates of various sizes, including flat substrates, especially on cut glass plates, or preferably on-line on a continuous glass ribbon during the float glass production process. Therefore, it is preferred that the method is performed online during the float glass production process, and the substrate is a glass ribbon. If the method is performed online, it is preferably performed on a glass ribbon in a float bath.

One advantage of performing this method online is that the coating deposited online is often durable, especially with good wear resistance and chemical resistance.

The in-line deposition method is preferably carried out under atmospheric pressure, and other deposition methods can also be carried out under atmospheric pressure.

In a particularly preferred embodiment, a method for producing durable photocatalytically active coated glass is provided, which includes depositing a photocatalytic activity on the surface of the glass substrate by contacting the surface of the substrate with a fluid mixture containing a titanium source Titanium oxide layer, the substrate surface temperature is in the range of 645°C to 720°C, preferably 670°C-720°C_o As mentioned above, the applicant has discovered that by depositing titanium oxide at high temperatures, it is possible to produce a coating with higher photocatalytic activity for its thickness. Since a coating with a reduced thickness tends to have a lower reflectivity, The present invention also provides high photocatalytic activity and medium or low photoreflection

200810002407.2 A new product with favorable combination of firing rate.

Therefore, in another aspect, the present invention provides a photocatalytically active coated substrate, including a substrate having a photocatalytically active titanium oxide coating on one surface thereof, characterized in that the coated surface of the substrate has a thickness greater than δχΙΟ ^ιη ^πιίη ¹The photocatalytic activity of the coated substrate, and the visible light reflectance measured on the coated side of the coated substrate is 35% or less.

High photocatalytic activity is advantageous because the amount of contaminants (including contaminants) on the coated surface of the photocatalytically active coated substrate decreases faster than on a substrate with lower photocatalytic activity. At the same time, faster removal of surface contaminants often occurs under low UV light intensity.

Pass at the strength of about 32W/m², The ultraviolet light of a UVA lamp with a peak wavelength of 351 nanometers is irradiated under the surface of the coated substrate, and the reduction rate of the integrated absorption rate of the infrared absorption peak corresponding to the C-Η stretch of the stearic acid film formed on the coated substrate is measured. Determine the photocatalytic activity used in this book. Stearic acid can be formed on the coated substrate by spin-casting a methanol solution of stearic acid, as described below.

Preferably, the photocatalytic activity of the coating surface of the substrate is greater than 1x10^cmTmirfi, more preferably greater than δχΙΟ ^οιη-^ΐη·¹.

Low visible light reflectivity is advantageous because it is less disruptive than high reflectivity, especially for glass substrates. Low visible light reflectivity corresponds to high visible light transmittance. This is used in glass construction, especially in automobiles. It is often required in aspects of the application.

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

In the most preferred embodiment of the present invention, the substrate is substantially transparent. In a preferred embodiment of the present invention, the substrate includes a glass substrate. Generally, the glass substrate is a soda lime silica glass substrate.

When the substrate is a soda lime silica glass substrate or other substrates containing alkali metal ions, the coated substrate preferably has an alkali metal ion barrier layer between the surface of the substrate and the photocatalytically active titanium oxide coating. This reduces the tendency of alkali metal ions to migrate from the substrate into the photocatalytically active titanium oxide coating, which is advantageous because it is well known that alkali metal ions have a tendency to poison the semiconductor oxide coating and reduce its activity.

The alkali metal ion barrier bottom layer may contain a metal oxide, but preferably an alkali metal

200810002407.2 The first ion blocking bottom layer is a silicon oxide layer. Silicon oxide may be silicon dioxide, but need not be stoichiometric, and may contain impurities such as carbon (often called silicon oxycarbide and deposited as described in GB2,199,848B) or nitrogen (often called silicon oxynitride).

Advantageously, the alkali metal ion barrier bottom layer is so thin that it has no significant impact on the optical properties of the coating, especially when the transparency of the transparent coated substrate is reduced or interference colors are generated in reflection or transmission. The appropriate thickness range will depend on the properties of the material used to form the alkali metal ion barrier layer (especially its refractive index). However, the thickness of the alkali metal ion barrier layer is generally less than 60 nanometers, preferably less than 40 nanometers. The alkali metal ion barrier layer, when present, should always be thick enough to reduce or prevent the migration of alkali metal ions from the glass into the titanium oxide coating.

One advantage of the present invention is that the photocatalytically active titanium oxide coating is thin (which is beneficial to lower the visible light reflectivity of the coated substrate), but the coated substrate still has excellent photocatalytic activity. Preferably, the thickness of the titanium oxide coating is 30 nanometers or less, more preferably, the thickness of the titanium oxide coating is 20 nanometers or less, and most preferably, the thickness of the titanium oxide coating is in the range of 2 to about 20 nanometers. Inside.

The present invention is also advantageous because fewer precursors are required to deposit a thin titanium oxide coating and the coating can be deposited in a shorter time. Thin titanium oxide coatings are also unlikely to produce interference colors in reflection or transmission. However, the special advantage is the low visible light reflectivity of the thin titanium oxide coating, which is particularly important when the coated substrate is coated glass. Generally, the visible light transmittance required by the coated glass will determine the thickness of the titanium oxide coating.

Preferably, the plated surface of the substrate has 20. Or smaller hydrostatic contact angle. The freshly prepared or cleaned glass surface has a hydrophilic surface (the hydrostatic contact angle is less than about 40°, indicating a hydrophilic surface), but organic contaminants quickly adhere to the surface to increase the contact angle. The special advantage of the coated substrate (especially coated glass) of the present invention is that even if the coated surface is contaminated, irradiating the coated surface with appropriate wavelength ultraviolet light can reduce or destroy those contaminants and reduce the contact angle. Another advantage is that the water spreads on the low contact angle surface, reducing the disturbing effect of water droplets (such as from rain) on the surface, and tends to wash away any dirt or other pollutants that are not destroyed by the photocatalytic activity of the surface . The static water contact angle is the angle that the meniscus of the water droplets on the glass surface faces. It can be determined by measuring the diameter of a water droplet of a known volume on the glass surface using a known method and calculated using an iterative method.

Preferably, the haze of the coated substrate is 1% or lower, which is advantageous because it can

200810002407.2 First, make the field of vision through the transparent coated substrate clear.

In a preferred embodiment, the coating surface of the substrate is wear-resistant, so that the coating surface maintains the photocatalytic activity after the reciprocation of the European standard abrasion test for 300 times. Preferably, the coating surface maintains photocatalytic activity after 500 reciprocations of the European standard abrasion test. More preferably, the coating surface maintains photocatalytic activity after 1,000 reciprocations of the European standard abrasion test.

This is advantageous because the self-cleaning coated substrate of the present invention is usually used when the coated surface is exposed to the outside (for example, the coated glass surface is used as the coated glass on the outer surface of the window). At this time, the coating is susceptible to wear.

The European standard abrasion test refers to the abrasion test described in the second part of the European standard BS EN 1096 (1999), including the felt pad reciprocating on the surface of the sample at a determined speed and pressure.

In this article, if you pass the European abrasion test, use ultraviolet light (for example, the peak wavelength is 351 nm) to reduce the static water contact angle to 15. Hereinafter, the coated substrate is considered to maintain photocatalytic activity. In order to obtain this contact angle, after the coated substrate is worn out, it usually needs less than 48 hours of irradiation, and the intensity at the surface of the coated substrate is about 32W/m².

Preferably, the haze of the coated substrate is 2% or less after passing through the European standard abrasion test.

The durable coated substrate according to the present invention is also durable against moisture circulation (it is assumed that this has a similar effect to weathering). Therefore, in a preferred embodiment of the present invention, the coated surface of the substrate is durable against moisture cycling, so that the coated surface maintains photocatalytic activity after the coated substrate undergoes 200 moisture cycling tests. In this text, the humidity cycle test refers to the temperature cycle in which the coating passes 35°C to 75°C and then to 35°C within 4 hours at a humidity close to 100°C. If after the test, reduce the static water contact angle to 15 by ultraviolet light irradiation. Hereinafter, the coated substrate is considered to maintain photocatalytic activity.

In another preferred embodiment, the present invention provides a durable photocatalytically active coated glass, comprising a glass substrate with a coating on one surface thereof, the coating including an alkali metal ion blocking bottom layer and photocatalytic activity Titanium oxide layer, in which the coating surface of the substrate is wear-resistant, so that the coating surface maintains the photocatalytic activity after going through 300 reciprocations of the European standard test. In this embodiment, the coated glass preferably has a visible light reflectance measured on the coated side of 35% or less, and the photocatalytically active titanium oxide layer preferably has a thickness of 30 nanometers or less.

200810002407.2 The thinnest coating is wear-resistant, which is unexpected, because it was previously thought that only thicker coatings have good durability.

In still another embodiment, the present invention provides a coated glass comprising a glass substrate with a photocatalytically active titanium oxide coating on one surface thereof, characterized in that the photocatalytic activity of the coated surface of the glass is greater than 4×10%ιηΤπιϊ_ηΤ, Preferably it is greater than βχΙΟ^αη^ιηίη¹, More preferably greater than exlO^cm^niin-¹, And the visible light reflectance of the coated glass measured on the coated side is less than 20%.

The coated substrate according to the present invention has applications in many fields, for example, as a window glass installation including a multi-layer window glass unit, a window glass panel including a first coating substrate in a spaced relationship with a second window glass panel, or when When the coated substrate is coated glass, as laminated glass, it includes a first glass plate layer (ply) of the coated glass, a polymer intermediate layer (for example, polyvinyl butyral) and a second glass plate layer.

In addition to its use in self-cleaning substrates (especially self-cleaning glass for windows), the coated substrate of the present invention can also be used to reduce the concentration of atmospheric pollutants. For example, coated glass under ultraviolet wavelengths (including ultraviolet wavelengths present in sunlight) can destroy atmospheric pollutants, such as nitrogen oxides, ozone, and organic pollutants adsorbed on the coated surface of the glass. This use is particularly advantageous in open areas in construction areas (for example, in urban streets), where the concentration of organic pollutants may be relatively high (especially in strong sunlight), but the available glass surface area of this place It is also relatively high. Alternatively, coated glass (with a coated surface on the inside) can be used to reduce the concentration of air pollutants inside buildings, especially in office buildings with high concentrations of air pollutants.

The present invention is illustrated by the following drawings but is not limited to the following drawings.

Fig. 1 is a graph showing the relationship between the photocatalytic activity of the coated glass produced by the method according to the present invention and the thickness of the titanium oxide coating.

Figure 2 shows an apparatus for on-line chemical vapor deposition of coatings according to the present invention.

In FIG. 1, the in-line CVD method described in the following examples is used to produce coated glass. Open circle 1 refers to a titanium oxide layer deposited using titanium tetrachloride as a titanium precursor, and cross number 2 represents a titanium oxide layer deposited using titanium tetraethoxide as a titanium precursor.

The coating can be applied to the glass substrate online by chemical vapor deposition during the glass manufacturing process

200810002407.2 first. Figure 2 shows a device for on-line production of coated glass products of the present invention, generally shown at 10, including a float part 11, a glass annealing furnace 12, and a cooling part 13. The float part 11 includes a molten tin bath 15 The bottom 14, the kiln roof 16, the side walls (not shown) and the end walls 17 together form a closed part, thereby providing a closed area 1 & wherein a non-oxidizing atmosphere is maintained to prevent oxidation of the tin bath 15. During the operation of the equipment 10, the molten glass 19 is cast on the hearth 20, and then flows under the metering wall 21, and then flows down to the surface of the tin bath 15, forming a discharge through the raised spokes 22 and through the retreat The furnace 12 is conveyed and then passed through the float glass ribbon 37 of the cooling section 13.

A suitable gas, such as a gas containing nitrogen and 2% by volume of hydrogen, is introduced into the region 18 through a conduit 23 connected to the manifold 24, so as to maintain a non-oxidizing atmosphere in the float section 11. At a speed sufficient to compensate for the gas loss (part of the non-oxidizing gas leaves the area due to flowing out under the end wall introduce non-oxidizing gas from the duct 23 to the area 18, and maintain a slight positive pressure higher than the ambient pressure. Tin bath 15 and The enclosed area 18 is heated by downward radiant heat from the heater 25. The heating area 18 is generally maintained at a temperature of about 1330-1400°F (721°C-760°C). The gas in the annealing furnace 12 is usually Air, the cooling area 13 is not sealed. The ambient air is blown on the glass by a fan 26.

The equipment 10 also includes coating machines 27, 2 & 29, and 30, which are connected in series on the float glass ribbon 37 in the float area 11. The precursor gas mixture for each coating is supplied to each coating machine, and the coating machine in turn directs the precursor gas mixture to the hot surface of the float glass ribbon 37. The temperature of the float glass ribbon 37 is highest at the coating machine 27 closest to the hearth 20 and lowest at the coating machine 30 closest to the annealing furnace 12.

The present invention is also illustrated by the following examples, in which, during the glass production process, the coating is applied to the moving float glass ribbon by laminar flow chemical vapor deposition in the float bath. In these examples, two coatings were applied to the glass ribbon.

Unless otherwise stated, all gas volumes are measured at standard temperature and pressure. A high-resolution scanning electron microscope and an optical model of the reflection and transmission spectra of the coated glass were used to determine the thickness of the coating. The measurement error of the coating thickness is about 5%. The transmission and reflection properties of the coated glass were measured using Hitachi U-4000 spectrophotometer. The a, b, and L* values of the transmission and/or reflection color of the glass mentioned herein refer to the CIE Lab color. Use D65 light source and according to ISO 9050 standard (Parry

200810002407.2 No.

Moon air mass (airmass) 2) standard CIE 2. The observer determines the visible light reflection and visible light transmission of the coated glass. Use WYK-Gardner Hazeguard+ haze meter to measure the haze of coated glass.

The photocatalytic activity of the coated glass is determined from the reduction rate of the infrared peak area corresponding to the C-H expansion and contraction of the stearic acid film on the glass coating surface under UVA light irradiation. 8xl0 by spin-casting 20 microliters of stearic acid in methanol on the surface of the glass coating at a speed of 2000 rpm³Mol/L) A thin film of stearic acid is formed on the glass sample (7-8 cm square), and the spin casting time is 1 minute. Measure the infrared spectrum in the transmitted light, measure the peak height of the peak corresponding to the C-H stretch (approximately 2700 -3000 cm-1) of the stearic acid film, and determine the corresponding peak area from the normalized curve of the peak area to the peak height. The coated side of the glass is irradiated with a UVA-351 lamp (obtained from Q-Panel Co., Cleveland, Ohio, USA) with a peak wavelength of 351 nm. The intensity at the surface of the coated glass is about 32W/D1²., Photocatalytic activity in this text or expressed as IR peak (using cm^min¹The area reduction rate expressed in units of ), or expressed as tgo% (in minutes), tgaze intently is the UV required to reduce the peak height (absorption) of the peak in this wavelength region to 10% of its initial value Light exposure time.

After irradiating the coated glass with a UVA 351 lamp for about 2 hours (or according to other instructions), the static water contact angle of the coated glass is determined by measuring the diameter of the water droplet (volume in the range of 1-5 microliters) placed on the surface of the coated glass.

Examples 1-15 A 1 mm thick soda-lime-silica float glass ribbon advancing at an annealing furnace speed of 300 m/h passes through a float bath at a position where the glass temperature is in the range of about 650°C-670°C , Apply two layers of coating. The atmosphere of the float bath contains a flowing gas mixture of nitrogen and 9% hydrogen, and the bath pressure is about 0.15 mbar.

Layer 1 (the first layer deposited on glass) is a silicon oxide layer. Use the coating equipment described in GB Patent 1 507 966 (specifically refer to Figure 2 and the corresponding description on page 3, line 73 to page 4, line 75), by making monosilane (SiH₄, 60 ml/min). Oxygen (120 ml/min). A gas mixture of ethylene (360 ml/min) and nitrogen (8 liters/min) contacts and flows parallel to the glass surface in the direction of glass movement to deposit layer 1 , The flow distance of the gas mixture on the glass surface is about 0.15 meters. The extraction pressure is approximately 0.9-1.2 mbar. At its temperature of about 670°C

200810002407.2 At the No. position, apply a glass ribbon to a width of about 10 cm. The thickness of the silicon dioxide layer is about 20-25m. Layer 2 (the second layer deposited) is a titanium dioxide layer that contains titanium tetrachloride in a flowing nitrogen carrier gas and ethyl acetate in a flowing nitrogen carrier gas. A separate gas flow of ester and a total nitrogen flow of 8 Ι/min (measured at 20 psi) is mixed into a gas mixture, and then the gas mixture is sent (through a pipeline maintained at about 250°C) by oil-cooled two-fluid coating Layer 2 is deposited in the coating equipment composed of the machine. The pressure of the nitrogen carrier gas and the total nitrogen flow is approximately 20 psi. The gas mixture flows countercurrently and downstream along the glass ribbon in contact and flow parallel to the glass surface. The downstream flow path of the gas mixture is about 0.15 meters, the countercurrent flow path is about 0.15 meters, and the extraction pressure is about 0.15 mbar. The nitrogen gas is passed through a bubbler containing titanium tetrachloride or ethyl acetate, and titanium tetrachloride and ethyl acetate are entrained in a separate flowing nitrogen carrier gas stream. The flow rate of the nitrogen carrier gas is as described in Table 1 (flow rate measured at 20 psi). Keep the titanium tetrachloride bubbler at 69. . The temperature of the ethyl acetate bubbler is kept at 42°C. For each of Examples 1-15, the estimated flow rates of entrained titanium tetrachloride and entrained ethyl acetate are also described in Table 1.

Measure the properties of the two-layer coating. For Examples 1-15, Table 2 describes the thickness of layer 2 (titanium oxide layer), and the value of visible light reflectance measured on the coating side, the L* and the fog of the coated glass degree. The haze of every kind of coated glass is lower than 0.2%.

Measure the photocatalytic activity and static water contact angle of coated glass. Table 3 describes the initial peak height and initial peak area, photocatalytic activity, static water contact angle, and thickness of the titanium oxide layer in the mouth corresponding to the IR peaks of stearic acid CH stretching of Example 1 15 unexpectedly. The photocatalytic activity has little effect.

Examples 16-19 Examples 16-19 were carried out under the same conditions as Examples 1-15, but the tank pressure was about 0.11 mbar, and the extraction pressure for the deposition of the silicon dioxide bottom layer (layer 1) was about 0.7 mbar. The titanium tetrachloride bubbler is maintained at a temperature of about 100 °C, the ethyl acetate bubbler is maintained at a temperature of about 45 °C, and the transfer line is maintained at a temperature of about 220°C.

In Table 1, for each of Examples 16-19, the flow rate of nitrogen carrier gas and the estimated flow rate of entrained titanium tetrachloride and entrained ethyl acetate are published.

For Examples 16-19, the estimated thickness value of layer 2 (titanium oxide layer), the visible light reflectance value measured on the coated side, the L* and the haze of the coated glass are described in Table 2.

200810002407.2 Table 3 describes the initial peak height and initial peak area, photocatalytic activity, t and static water contact angle of each of Examples 16-19 corresponding to the IR peaks of stearic acid C-H stretching .

The photocatalytic activity of Examples 16-19 is not significantly greater than that of Examples 1-15, although the titanium oxide coating is thicker (and therefore the reflectivity is higher).

200810002407.2 Table 1

<td>Example</td><td colspan="2">Nitrogen carrier gas flow to the bubbler (L/min, measured at 20psi)</td><td rowspan="2">ΙΪΟ4 flow (liter/side)</td><td rowspan="2">Ethyl acetate flow rate (l/min)</td>

<td></td><td>nq station</td><td>Ethyl acetate bubbler</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 j</td><td>0.14</td>

<td>3</td><td>0」2</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」6</td>

<td>19</td><td>0.04</td><td>0.2</td><td>0.035</td><td>0.11</td>

200810002407.2 Table 2

<td>Example</td><td>Degree (nm)</td><td>JLiUX%)</td><td>L* value of coated glass (%)</td><td>Haze (%)</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>11.4</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>a</td><td>a</td><td>0.07</td>

<td>7</td><td>8</td><td>a</td><td>a</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>&amp;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>a</td><td>a</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」</td>

<td>16</td><td>a</td><td>2&amp;4</td><td>47.8</td><td>0.3</td>

<td>17</td><td>ca 68</td><td>29.1</td><td>58.4</td><td>0.37</td>

<td>18</td><td>ca 32</td><td>25.9</td><td>55.6</td><td>0.24</td>

<td>19</td><td>ca 27</td><td>20.5</td><td>50.2</td><td>0.2</td>

a

200810002407.2 Section 3

<td rowspan="2">Example</td><td colspan="2">IR peak of ch forest melted in Liwa (2700-3000cm7)</td><td rowspan="2">Lateralization activity (X 10'²cm⁴min'¹)</td><td rowspan="2">Melting angle (°)</td><td rowspan="2">^&gt;0% (pink</td>

<td>High&gt;</td><td>Initial 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 Soil 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>

200810002407.2 Examples 20-27 were carried out under the same conditions as Examples 1-15, but the difference was that the carrier gas was passed through a bubbler containing titanium tetraethoxide maintained at a ratio of 170. The layer 2 is deposited with a gas mixture of titanium tetrachloride entrained in a nitrogen carrier gas. For each of Examples 20-27, the nitrogen carrier gas (measured at 20 psi) and the flow rate of titanium tetraethoxide are described in Table 4. The flow rate of the overall nitrogen is 8.5 l/min (measured at 20 psi).

Measure the performance of the two-layer coating. For each of Examples 20-27, Table 5 describes the thickness value of layer 2 (titanium oxide layer), the visible light reflectance value measured on the coated side, and the haze of the coated glass. The haze of each coated glass is less than 0.7%.

Measure the photocatalytic activity and static water contact angle of coated glass. Table 3 describes the initial peak height and initial peak area, photocatalytic activity, seven-wheel drive, and static water contact angle of the IR peak corresponding to stearic acid C-H stretch for each of Examples 20-27.

Examples 28 and 29 Examples 28 and 29 were performed under the same conditions as in Examples 20-27, but the difference was that the titanium tetraethoxide bubbler was maintained at a temperature of 168 ° C, and the tank pressure was 0.11 mbar . Tables 4, 5 and 6 describe the relevant data of Examples 28-29 corresponding to Examples 20-27.

200810002407.2 Section 4

<td>Example</td><td>Ammonia carrier gas to the titanium tetraethoxide bubbler. Flow KL/min, measured at 20psi)</td><td>(Liter/Minute)</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>0.4 |</td><td>0.020</td>

table 5

<td>Example</td><td>Thickness (nm)</td><td>Can beΧΛΟΗ%)</td><td>Haze %)</td>

<td>20</td><td>13</td><td>a</td><td>0.4</td>

<td>21</td><td>13</td><td>a</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>a</td><td>0.28</td>

<td>24</td><td>24</td><td>a</td><td>a</td>

<td>25</td><td>26</td><td>a</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>3&amp;3</td><td>35.2</td><td>0.29</td>

<td>29</td><td>31.9</td><td>2&amp;4</td><td>0.22</td>

a not measured

200810002407.2 Section 6

<td rowspan="2">Example</td><td colspan="2">IR peak of C-HW (2700-3000cm'¹)</td><td rowspan="2">Peach activity (χ ΙΟ' αη^πώα¹)</td><td rowspan="2">Tentacle (°)</td><td rowspan="2">W14(State 1[</td>

<td>Initial peak height (absolute</td><td>Initial 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>a</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>7.1</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

200810002407.2 Examples 30-42 In Examples 30-42, in the float glass production process, two layers of coating were applied to the entire width of about 132 inches (3.35 m) by in-line CVD in the float bath Coated on float glass ribbon. The equipment used to deposit the coating is illustrated in FIG. 2. The atmosphere of the float bath contains nitrogen and 2% by volume of hydrogen. The tank pressure is 0.15 mbar.

The two-layer coating consists of a silicon oxide layer first deposited on the float glass ribbon and a titanium oxide layer deposited on the silicon oxide layer. The precursor chemical composition of the gas mixture used to deposit the coating was the same as that used in Examples 1-15. The deposition temperature of the coating was changed by using different coaters 27, 2 &amp; 29 or 30 (refer to FIG. 2). The coating machine 27 closest to the hearth is the hottest, and the coating machine 30 closest to the annealing furnace is the coolest. In Examples 30 to 33 and 42, two coating machines (28 and 29 in Examples 30 to 33, and coating machines 27 and 28 in Example 42) were used to deposit the silicon oxide layer. The advantage of using two coaters to deposit the silicon oxide layer is that longer production run times are possible.

For Examples 30-41, the gas mixture used to deposit the silicon oxide layer consisted of the following gases at the following flow rates: nitrogen (250 1/min), nitrogen (285 1/min), monosilane (2.5 1/min), Ethylene (15 Ι/min) and oxygen (10 Ι/min). For Example 42, except for monosilane (2.3 Ι/min), ethylene (13.8 Ι/min) and oxygen (9.2 Ι) /min), use the same gas and flow rate. In the case where two coaters were used to coat the silicon oxide layer in Examples 30 to 42, the above-mentioned flow rate was used for each coater.

In Examples 30-42, the deposition temperature (that is, the temperature of the float glass ribbon corresponding to each coating machine 27 to 30 under the coating machine) is as shown in Table 7. The temperature error in Table 7 is about ±50 taps (±28°0. The extraction pressure of each coating machine is about 2 mbar.

Table 7

<td>Machine</td><td>Qing brought</td>

<td>27</td><td>1330°F (721°C)</td>

<td>28</td><td>1275°F (690°C)</td>

<td>29</td><td>1250°F (677°C)</td>

<td>30</td><td>1150°F (621 °C)</td>

Titanium Tetrachloride (TiCl₄) And ethyl acetate are entrained in a separate nitrogen/ammonia carrier gas stream. For Ding Zhiwei's evaporation, a thin film evaporator is used. Liquid TiCl₄Keep in a pressurized container (pressure head approx.

200810002407.2 No.

5psi)_oThis is used to deliver liquids to metering pumps and Coriolis force flow measurement systems. The metered precursor stream is then sent to a thin film evaporator at a temperature of 110°F (43°C). Then, T1C1₄It is entrained in the carrier gas (ammonia) and sent to the mixing point downline maintained at 250 °F (121 °C). Ethyl acetate is delivered in a similar way. The liquid ethyl acetate is kept in a pressure vessel (pressure head is about 5 psi). This is used to deliver the liquid to the metering pump and the Coriolis force flow measurement system. Then, the metered precursor stream is sent to a thin film evaporator at a temperature of 268°F (131°C). The evaporated ethyl acetate is then entrained in the carrier gas (ammonia/nitrogen mixture) and sent to the downstream line at a mixing point maintained at about 250°F (121°C). The TiCg and ethyl acetate gas streams are mixed to form a gas stream for deposition. Gas mixture of titanium oxide layer. The mixing point is just before the coater.

For Examples 30-42, the linear velocity of the float glass ribbon, the deposition temperature of silicon oxide and the deposition temperature of the titanium oxide layer, and the flow rate of He/% total carrier gas and TiCl are described in Table 8.₄And the flow of ethyl acetate.

The coated float glass ribbon is cooled and cut, and the optical properties and photocatalytic activity of the sample are measured. Table 9 describes the haze, the optical properties in the transmission and reflection of the sample (percent visible light transmittance/reflectance and color coordinates using the LAB system). The coated glass undergoes abrasion test according to BS EN 1096, in which a sample with a size of 300nnnx300mm is rigidly fixed on the test bench at the four corners to ensure that the sample cannot be moved. Cut the unused felt pad to the size described in the standard (BS EN 1096 Part 2 (1999)), then install it on the test robot finger and lower the robot finger to the glass surface. Then set a load pressure of 4N on the test robot finger and start the test. Make the mechanical finger reciprocate 500 times on the sample at a speed of 60 reciprocations/min±6 reciprocations/min. When the abrasion is completed, the sample is removed, inspected optically, and inspected with photocatalytic activity. If the wear produces a transmittance change of no more than ±5% when measured at 550 nm and the coated substrate maintains the photocatalytic activity, that is, after the test, irradiating with ultraviolet light for 2 hours can reduce the static water contact angle to 15. , It is considered that the sample has passed the test.

The glass has also undergone a humidity cycle test, in which the coating undergoes a temperature cycle of 35°C to 75°C and then to 35°C within 4 hours at close to 100% relative humidity.

Table 10 describes the production state and 130 minutes of ultraviolet light irradiation (UVA 351mm lamp, about 32W/m²) And after 300, 500 and/or 1000 cycles of European standard abrasion test

200810002407.2 The static water contact angle of the first coated glass. The contact angle of the abraded sample was measured after 2 hours of irradiation.

Specimens deposited at higher temperatures of 1330-1250°F (721 °C-677°C) are still photocatalytically active even after 1,000 cycles of European standard abrasion or 200 cycles of moisture. Table 11 describes the photocatalytic activity of the coated glass in the production state after 300, 500 and/or 1000 cycles of the European standard abrasion test and after 200 cycles of the moisture cycle test. In Table 11, the term activity means that the coated glass is photocatalytically active, but t has not been determined_90%.

200810002407.2 No.

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200810002407.2 No.

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200810002407.2 Table 10

<td rowspan="2">Example</td><td colspan="5">Hydrostatic contact angle after deletion at a certain number of reciprocations (°)</td>

<td>0</td><td>0 (UV radiation 130 but middle and rear)</td><td>300</td><td>500</td><td>1000</td>

<td>30</td><td>2.3</td><td>3.3</td><td></td><td></td><td></td>

<td>31</td><td>2.0</td><td>3.2</td><td></td><td></td><td></td>

<td>32</td><td>a</td><td>a</td><td></td><td></td><td></td>

<td>33</td><td>2.0</td><td>3.2</td><td></td><td></td><td></td>

<td>34</td><td>a</td><td>a</td><td></td><td></td><td></td>

<td>35</td><td>2.0</td><td>- 3.2</td><td></td><td></td><td></td>

<td>36</td><td>2.1</td><td>3.4</td><td></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

200810002407.2 Section 11

<td rowspan="2">Example</td><td colspan="4">The city after a certain reciprocating fine wear and tear (minutes)</td><td rowspan="2">200 torch heart lying like (minutes)</td>

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

<td>30</td><td>7.5</td><td></td><td></td><td></td><td></td>

<td>31</td><td>1&amp;5</td><td></td><td></td><td></td><td></td>

<td>32</td><td>8.5</td><td></td><td></td><td></td><td></td>

<td>33</td><td>8 .</td><td></td><td></td><td></td><td></td>

<td>34</td><td>21</td><td></td><td></td><td></td><td></td>

<td>35</td><td>4</td><td></td><td></td><td></td><td>^Jrt</td>

<td>36</td><td>&amp;5</td><td></td><td></td><td></td><td></td>

<td>37</td><td>15.5</td><td></td><td>Approximately 2160</td><td></td><td>active</td>

<td>38</td><td>18.5</td><td></td><td>Approx. 2160</td><td></td><td>active</td>

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

<td>40</td><td>18.5</td><td></td><td>Easy 2160</td><td></td><td>active</td>

<td>41</td><td>a</td><td></td><td></td><td>Approximately 2160</td><td>active</td>

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

a not measured

200810002407.2