Blue privacy glass

The object of the invention is a glass composition, tinted blue, absorbing red and violet radiation, based on sdDecalciumquartz glass, and its use.

This type of glass has a low light transmittance, which makes it desirable for use as insulating glazing in vehicles, such as side and rear windows in vans or solar panels in automotive vehicles. It is understood that the term "tinted blue" as used herein encompasses glasses which have a predominant wavelength of 0 0 8P 0 089 nanometers (nm) and may also be characterized as blue-green or blue-gray colored glasses. The glasses should also have lower transmittance of red and light rays compared to the typical blue glasses used in motor vehicles and be compatible with the methods of producing fleet glass.

Various compositions of dark colored glass absorbing red and violet radiation are known in the art. The primary dye in typical dark tinted glass insulating glasses is iron, which is usually

190 730 present as both Fe2O3 and FeO. Some glasses use cobalt, selenium, and optionally nickel in combination with iron to achieve the desired color and absorb infrared and ultraviolet radiation, as disclosed in US Patent Nos. 4,873,206 to Jones, US 5,278,108 to Cheng et al. ., US 5,308,805 to Baker et al., US 5,393,593 to Gulott et al., US 5,545,596 and US 5,582,455 to Casari et al., And European Patent Application No. EP 0705800. Other glasses also contain chromium in combination with dyes, as disclosed in US Patent Nos. 4,104,076 to Pons, US 4,339,541 to Dela Ruye, US 5,023,210 to Krumwiede et al. and US 5,352,640 to Combes et al., and European Patent Application No. EP 0536049, French Patent No. FR 2331527 and Canadian Patent No. CA 2,148,954. From patents such as U.S. Patent Nos. 5,521,128 and 5,346,867 to Jones et al. and US 5,411,922 to Jones, manganese and optionally titanium are further known. Still other glasses may contain additional materials, such as are known from International Publication No. WO 96/00194, which discloses the inclusion of fluorine, zirconium, zinc, cerium, titanium and copper in the glass composition, requiring that the sum of the earth metal oxides alkali was less than 10% by weight of the glass.

U.S. Patent No. 4,792,536 to Pecoraro et al. discloses one particular composition which provides superior spectral properties. In-market products made under this patent are sold by PPG Industries, Inc. under the trade names SOLEXTRA® and AZURLITE®. Such glass has a predominant wavelength in the range of about 486 to 489 nm and an excitation purity of about 8 to 14%. It would be desirable to have a dark tinted blue colored glass that can be used as environmental insulating vehicle glazing to complement the blue tinted glass available in cars and vans with higher solar performance and which is compatible with commercial fleet glass manufacturing techniques.

According to the invention, a glass composition, tinted blue, absorbing infrared and ultraviolet radiation, which comprises a part of a base glass, containing:

S1O2 from 66 to 75% by weight

Na2O from 1 to 2d% by weight

CaO from 5 to 15% by weight

MgO from 0 to 55% by weight

Al2Os from 0 to 55% by weight

K2O from 0 to 55% w / w is characterized in that it also comprises a coloring agent part which absorbs solar radiation, essentially consisting of:

total iron from 0.9 to 2% by weight

FeO from 0.15 to 0.65% by weight

CoO from 90 to 250 ppm

T1O2 from 0.02 to 0.40% by weight

Se from 0 to 12 ppm, and

MnO2 from 0 to 39 pdm, the glass has a LTA light transmittance of more than 20% to 60%, and the color of the glass is determined by the predominant wavelength ranging from 480 to 489 nanometers and excitation purity of at least 8%, in addition, the glass has a total a transmittance of solar ultraviolet radiation TSUV 35% or less, all of the above factors being measured at a glass thickness of 4.06 mm. Preferably in this composition the concentration of total iron is from 1 to 1.4% by weight, the concentration of FeO is from 0.20 to 0.50% by weight and the concentration of CoO is 100 to 150 ppm. Preferably, the composition has a redox index of from 0.20 to 0.35.

Preferably, in the composition according to the invention, the concentration of total iron is from 1.1 to 1.3% by weight, the concentration of FeO is from 0.24 to 0.40% by weight and the concentration of CoO is from 110 to 140 ppm.

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The glass obtained from the composition according to the invention preferably has a total solar infrared transmittance TSIR of 25% or less, and a total solar energy transmittance TSET of 40% or less, and the color of the glass is determined by the predominant wavelength in the range 482 to 487 nanometers and excitation purity 10 up to 30%.

Preferably, the glass obtained from such composition has a total solar ultraviolet transmittance TSUV of 30% or less, a total solar infrared transmittance TSIR of 20% or less, and a total solar infrared transmittance TSET 35% or less.

Preferably, the glass has a LTA light transmission of greater than 35 to 55%.

The glass prepared from the composition of the invention preferably has a total solar infrared transmittance TSIR of 25% or less, and a total solar infrared energy transmittance TSET of 40% or less.

More preferably, the glass has a LTA light transmission of greater than 35 to 55%.

Preferably, the color of the glass is defined by a predominant wavelength ranging from 482 to 489 nanometers and an excitation purity of 10 to 30%.

The composition according to the invention preferably has a redox index of 0.15 to 0.40.

In the composition according to the invention, the concentration of CoO is preferably from 90 to less than 200 ppm. Glass made from such composition has a LTA light transmittance of greater than 20 to 55%, a total solar infrared transmittance TSIR of 25% or less, and a total solar energy transmittance TSET of 40% or less, and the color of the glass is determined by a predominant wavelength ranging from 482 to 489 nanometers and excitation purity of 10 to 30%.

Preferably, such glass has a light transmittance ITa of more than 35 to 60%.

In such a composition according to the invention, the concentration of total iron is preferably from 1 to 1.4% by weight, the concentration of FeO is from 0.20 to 0.50% by weight, the concentration of CoO is from 100 to 150 ppm and the concentration of Se is from 0 to 8 ppm. The composition preferably has a redox index of from 0.20 to 0.35. In such a composition, the concentration of total iron is preferably from 1.1 to 1.3% by weight, the concentration of FeO is from 0.24 to 0.40% by weight and the concentration of CoO is from 110 to 140 ppm.

The composition according to the invention, in its coloring agents part, may additionally contain:

Sun₂O3 from Odo 1% by weight

SnO₂ from 0 to 2% by weight c0

ZnO from Odo 1% lvag

MoO3 from 0 to 0.03% by weight

CeO2 from 0 to 2% by weight, and

NiO from 0 to 0.1 wt%, wherein the glass has a LTA light transmittance of greater than 35% to 60%. Glass produced from such a composition has a total solar infrared transmittance TSIR of 25% or less, and a total solar infrared energy transmittance TSET of 40% or less. The color of such glass is preferably determined by the predominant wavelength in the range 482 to 487 nanometers and the excitation purity of 10 to 30%. Preferably in such a composition the concentration of total iron is from 1.0 to 1.4% by weight, the concentration of FeO is from 0.2 to 0.5% by weight, the concentration of CoO is from 100 to 150 ppm and the concentration of Se is from 0 to 8 ppm.

The composition may be in the form of a flat glass panel formed by a float process.

The composition according to the invention may also be substantially selenium-free, the glass produced therefrom having a LTA light transmittance of greater than 20% to 60%, or the CoO concentration is less than 200 ppm.

The glass composition according to the invention is applicable to the production of a flat glass panel by the float process. Preferably, flat glass panes made of it are used as glazing for car windows.

190 730

According to the invention, a further infrared and ultraviolet radiation-absorbing glass composition, tinted blue, which comprises a part of a base glass containing:

SiO₂ from 66 to 75% by weight

On₂O from W to 2d wt.% Rb

CaO from 5 dd) 105 wt.%

Give up the MgO% by weight

Al2O3 from d to 5% aooh

K.₂It is characterized by the fact that, in addition, it has a coloring agent part in its composition which absorbs solar radiation, essentially consisting of:

total iron from 0.0 to 0.3% by weight

FeO from 0.24 to 0.40% by weight

CoO from 110 to 0 opm

TiO2 from 0.02 to 0.40% by weight

Se from 1 to 6 ppm, and

MnCE from 0 to 39 ppm, whereby the glass has a LTA light transmittance of more than 35% to 00%, and the color of the glass is determined by a dominant wavelength ranging from 480 to 489 nanometers and excitation purity of at least 8%, all of the above indicators were determined for a glass thickness of 4.00 mm.

Glass produced from such a composition according to the invention preferably has a total solar infrared transmittance TSIR of 25% or less, and a total solar energy transmittance TSET of 40% or less, and the color of the glass is determined by the predominant wavelength in the range 482 to 487 nanometers and excitation purity. between 00 and 30%.

More preferably such glass has a total solar ultraviolet transmission TSUV of 30% or less, a total solar infrared transmission TSIR of 20% or less, and a total solar infrared transmittance TSET 35% or less. Even more preferably, such glass has a LTA light transmittance of 40 to 55%.

The glass produced from the composition of the invention preferably has a total solar infrared transmittance TSIR of 25% or less, and a total solar infrared energy transmittance TSET of 40% or less. Preferably, such glass has a light transmittance LTA of 40 to 55%. Preferably, the color of this glass is defined by a predominant wavelength ranging from 482 to 489 nanometers and an excitation purity of 00 to 30%.

Preferably, such a composition according to the invention has a redox index of from 0.05 to 0.40

The glass composition defined above is applicable to the production of a flat glass panes by the float process. Preferably, flat-glass panes made therefrom are used in the manufacture of car window glazing.

According to the invention, a blue-tinted ultraviolet and infrared absorbing glass composition has been developed which has a light transmittance of up to 00%. The glass uses a standard basic composition of soda-lime-quartz glass and additionally iron, cobalt and titanium and possibly selenium as materials absorbing infrared and ultraviolet radiation and as dyes. The color of the glass according to the invention has a predominant wavelength in the range of 480 to 489 nanometers and an excitation purity of at least 8% at a thickness of 0.000 inches (4.00 millimeters).

In one embodiment of the invention, the composition of a blue-tinted soda-lime and ultraviolet-silica absorbent soda-lime and ultraviolet glass product comprises a solar radiation-absorbing and coloring portion consisting essentially of 0.9 to 2.0 wt.% Total iron, from 0 0.05 to 0.05 wt% FeO, 90 to 250 ppm CoO, 0.02% to 0.40 wt% TiO2, and optionally 0 to 12 ppm Se and 0 to 39 ppm MnO2, preferably from 1 to 0 .4% by weight of total iron

190 730, from 0.20 to 0.50% by weight FeO, from 100 to 150 ppm CoO, from 0.02% to 0.40% by weight TiO2, and optionally up to 8 ppm Se.

The base glass according to the invention is a glass in which the main components of the glass without the infrared and ultraviolet radiation absorbing materials and possibly the dyes which are the subject of the present invention are commercial soda-lime-quartz glass with the following typical characteristics:

<td></td><td>Weight percentages</td>

<td>SiO2</td><td>66 »to 7 ^</td>

<td>Na2O</td><td>10 to 20</td>

<td>CaO</td><td>5 to 15</td>

<td>MgO</td><td>0 to 5</td>

<td>Al2O3</td><td>0 to 5</td>

<td>K2O</td><td>Odo 5</td>

As used herein, all "weight percent" (wt%) values ​​are based on the total weight of the final glass composition.

To this base glass, according to the invention, materials absorbing infrared and ultraviolet radiation and dyes in the form of iron, cobalt and titanium, and optionally selenium, are added. As disclosed herein with respect to glass compositions, iron is expressed as Fe2O3 and FeO, cobalt as CoO, titanium as TiO2, and selenium as elemental selenium. It should be clear that the described glass compositions may contain small amounts of other materials, for example melting and refining aids, incidental materials or impurities. Moreover, it should be evident that in one embodiment of the invention, small amounts of additional materials may be included in the glass to provide the desired color properties and to improve the solar properties of the glass, as will be explained in more detail hereinafter.

Iron oxides in the glass composition perform a number of functions. Ferric oxide, Fe2O3, is a strong absorber of ultraviolet radiation and acts as a yellow dye in glass. Ferrous oxide, FeO, is a powerful absorber of infrared radiation and acts as a blue dye. The total amount of iron present in the glasses disclosed herein is determined as Fe2O3 in accordance with standard analytical practice, but this does not mean that all iron is actually in the form of Fe2O3. Likewise, the amount of iron in the ferrous state is reported as FeO, although it need not actually be present in the glass as FeO. To represent the relative amounts of ferrous iron in the glass compositions disclosed herein, the term "redox" will mean the amount of iron in the ferrous state (expressed as FeO) divided by the amount of total iron (expressed as Fe2O3). Further, unless otherwise stated, the term "total iron" in this specification will mean total iron expressed as Fe2O3 and the term "FeO" will mean ferrous iron expressed as FeO.

Cobalt Co acts as a blue dye and does not show any particular properties of absorbing infrared or ultraviolet radiation. Selenium Se is an ultraviolet light absorbing pigment that gives a pink or brown color to soda lime quartz glass. Selenium Se can also absorb some infrared radiation and its use tends to reduce the redox index. TiO2 is an ultraviolet light absorber which acts as a dye to give the glass composition a yellow color. In order to obtain the desired blue colored glass insulating from the environment and having the desired spectral properties, a proper balance is required between iron, i.e. ferric and ferrous oxide, and cobalt, titanium and possibly selenium.

The glass of the present invention can be melted and refined in a continuous large-scale commercial glass melting operation and formed into variable thickness flat glass panes by a fleet process in which the molten glass is based on a molten metal, usually tin, where it takes the shape of a ribbon, and cooled as is well known in the art.

While it is preferred that the glass described herein be made using a conventional continuous fired melting operation well known in the art, the glass may be made well known in the art, the glass may also be produced using a multi-stage melting operation known in the art. U.S. Patent No. 4,381,934 to Kunkkle et al., US 4,792,536 to Pecoraro et al. and 4,886,539 to Cerutti et al. If necessary, a mixing system may be used in the melting and / or forming steps of the glass manufacturing operation to homogenize and produce glass with the highest quality of operations.

Depending on the type of melting operation, sulfur may be added to the charge materials of the soda lime-silica glass as a melting and refining aid. Commercial-manufactured fleet glass may contain up to about 0.3% by weight of SO3. In a glass composition that includes iron and sulfur, providing reducing conditions can result in an amber color that lowers light transmittance, as discussed in U.S. Patent No. 4,792,536 to Pecoraro et al. However, it is believed that the reducing conditions required to impart such color in float glass compositions of the type discussed herein are limited to approximately the first 0.020 mm of the bottom glass surface in contact with the molten tin during the float glass forming operation and to a lesser extent to the exposed top surface of the glass. Due to the low sulfur content of the glass and the limited area of ​​the glass in which the color cannot appear, depending on the particular composition of the soda-lime-quartz glass, the sulfur in these surfaces has essentially no material effect on the color of the glass or on the spectral properties.

It should be clear that by forming the glass on molten tin as discussed above, measurable amounts of tin oxide may migrate to the surface portions of the glass on the molten tin contact side. The piece of fleet glass typically has an SnO concentration₂ ranging from about 0.05 to 2% by weight in the first 0.025 mm approximately below the surface of the glass which has been in contact with the tin. Typical SnO background levels₂ they may be 30 parts per million (ppm). It is believed that high tin concentrations at approximately the first 0.000001 mm (10 Å) of the molten tin-based glass surface may slightly increase the reflectivity of that glass surface, but the overall effect on the glass properties is minimal.

Table 1 shows examples of experimental glass melts having compositions corresponding to the glass compositions of the present invention. Similarly, Table 2 lists a series of computer modeled glass compositions conforming to the principles of the present invention. Model compositions were produced on a computer model with programming for glass color and spectral properties, developed by PPG Industries, Inc. Tables 1 and 2 only list the iron, selenium and cobalt parts of the examples. Analysis of the selected experimental melts in Table 1 indicates that the molten products are expected to contain most likely up to about 10 ppm Cr₂ABOUT₃, up to about 39 ppm MnO₂. Examples 5-19 also contain up to about 0.032% by weight of TiO2. It is assumed that C2O3, MnO2 and TiO2 get into the molten glass as part of the glass cullet. In addition, model compositions were set up to introduce 7 ppm Cr2O₃. It is believed that the glass compositions of the invention produced by a commercial fleet process, as discussed earlier, may contain low levels of C2O3 and MnO2 and a little more than 0.020% by weight of TiO2, however, levels of such materials are considered to be accidental levels that do not affect. material to the color properties and the spectral properties of the blue glass according to the invention.

The spectral properties shown in Tables 1 and 2 are based on a standard thickness of 0.160 inches (4.06 mm). It should be clear that the spectral properties given in the examples can be approximated at various thicknesses using the formulas known from US 4,792,536.

Regarding the transmittance data of Table 1, the light transmittance (LTA) is measured using the CIE Illumination Standard "A" with a 2 ° observation unit in the wavelength range of 380 to 770 nanometers. The color of the glass with respect to the predominant wavelength and the purity of the excitation is measured using the CIE "C" illuminating standard with a 2 ° observation device according to the procedures set out in ASTM E308-90. Whole

190 730 solar ultraviolet radiation transmittance (TSUV) is measured in the wavelength range 300 to 400 nanometers, total solar infrared transmittance (TSIR) is measured in the wavelength range 720 to 2000 nanometers and total solar energy transmittance (TSET) is measured in the wavelength range from 300 to 2000 nanometers. The transmittance data of TSUV, TSIR and TSET are calculated using the data of direct solar radiation 2.0 irradiance from the Parry Moon air mass and integrated using the trapezoidal rule known in the art. The spectral properties shown in Table 2 are based on the same wavelength ranges and calculation procedures.

Preparation of samples

The information given in Table 1 of Examples 1-4 is based on experimental laboratory melts which approximately have the following input components:

<td></td><td>Examples 1-3</td><td>Example 4</td>

<td>Cullet A.</td><td>3000 g</td><td>2850 g</td>

<td>Cullet B.</td><td> -</td><td>150 g</td>

<td>TiO₂</td><td>6g</td><td>6g</td>

Cullet A contains about 1.097 wt.% Total iron, 108 ppm CoO, 12 ppm Se and 7 ppm Cr2O3. Cullet B contains about 0.385 wt.% Total iron, 67 ppm CoO, 12 ppm Se, and 8 ppm Cr2O3. To prepare the alloys, the ingredients were weighed, mixed, placed in a platinum crucible and heated to 2650 ° F (1454 ° C) for 2 hours. The molten glass was then irritated with water, dried and re-heated in a platinum crucible to temperature (1454 ° C) for 1 hour. The molten glass was then re-fritted in water, dried, and re-heated in a platinum crucible to 2650 ° F (1454 ° C) for 2 hours. The molten glass was then poured from the crucible to form a pane and annealed. Samples were cut from the panes, ground and polished for analysis.

The information given in Table 1 for Examples 5-19 is based on experimental laboratory melts which approximately have the following input components:

<td>Cullet</td><td>239.74 g</td>

<td>Sand</td><td>33,140 g</td>

<td>Ammonia soda</td><td>IO8225 g</td>

<td>Limestone</td><td>28.14 g</td>

<td>Dolomite</td><td>79.80 g</td>

<td>Technical sodium sulfate</td><td>2.32 g</td>

<td>Fe2O3 (total iron)</td><td>how many tzzeba</td>

<td>C63O4</td><td>lle cut</td>

<td>Se</td><td>He's a cut</td>

<td>TiO2</td><td>He must</td>

<td colspan="2">The raw materials were set to make the final glass weighing 700 grams. As</td>

as needed, reducing agents were added to adjust the redox index. The cullet used in the melt (which was approximately 30% of the molten material) contained up to 0.51 wt% total iron, 0.055 wt% TiO2, and 7 ppm Cr2O3. In making the melt, the ingredients were weighed and mixed, and then a portion of the raw feedstock was placed in a quartz crucible and heated to a temperature of 2,450 ° F (1,343 ° C). After the feed material had melted, the remaining raw materials were added to the crucible, and the crucible was held for 30 minutes at 2450 ° F (1343 ° C). The molten batch was then heated and held at 2500 ° F (1372 ° C), 2aa0 ° F (1399 ° C), 2600 ° F (1427 ° C) for 30 minutes, 30 minutes, and 1 hour respectively. The molten glass was then shredded in water, dried, and reheated to 2,650 ° F (1,454 ° C) for two hours in a platinum crucible. The molten glass was then poured from the crucible to form a sheet and annealed. Samples were cut from the panes, ground and polished for analysis.

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Chemical analysis of glass compositions (except for FeO) was carried out using a RIGAKU 3370 X-ray fluorescence spectrophotometer. The spectral properties of the glass were determined on annealed samples using a PerkinElmer Lambda 9 UV / VIS / NIR spectrophotometer before glass tempering or prolonged exposure to ultraviolet radiation, which affects the properties of the glass. spectral glass. FeO content and redox index were determined using a computer model with programming of glass color and spectral characteristics developed by PPG Industries, Inc.

The approximate basic oxides of the experimental melts presented in Table 1, calculated on the basis of the charge, are given below:

<td></td><td>Examples 1-3</td><td>Example 4</td><td>Examples 5-19</td>

<td>S1O2 (% by weight)</td><td> 66,10</td><td> 66,80</td><td> 72,400</td>

<td>On₂O (% by weight)</td><td> 17,80</td><td> 17,40</td><td> 13,500</td>

<td>CaO (% by weight)</td><td> 7,80</td><td> 7,90</td><td> 8,700</td>

<td>MgO (% by weight)</td><td> 3,10</td><td> 3,10</td><td> 3,700</td>

<td>Al₂O3 (% by weight)</td><td> 3,10</td><td> 2,80</td><td> 0,170</td>

<td>K2O (% by weight)</td><td> 0,70</td><td> 0,63</td><td> 0,049</td>

It is expected that the oxide components of the basic compositions of the commercial soda-lime-silica glass based on the experimental melts shown in Table 1 and the model compositions shown in Table 2 will be similar to those previously discussed.

Table 1

<td></td><td>Ex. 1</td><td>Pc. 2</td><td>Ex. 3</td><td>Ex. 4</td><td>Ex. 5</td><td>Ex. 6</td><td>Ex. 7</td><td>Ex. 8</td><td>Ex. 9</td><td>Ex. 10</td>

<td>Total iron (% by weight)</td><td> 1110</td><td> 1,116</td><td> 1,117</td><td> 1,044</td><td> 1,233</td><td> 1230</td><td> 1237</td><td> 1238</td><td> 1236</td><td> 1232</td>

<td>FeO (% by weight)</td><td> 0,389</td><td> 0,386</td><td> 0,394</td><td> 0,379</td><td> 0,317</td><td> 0,316</td><td> 0,329</td><td> 0,317</td><td> 0,304</td><td> 0,320</td>

<td>Redox model.</td><td> 0,350</td><td> 0,346</td><td> 0,353</td><td> 0,362</td><td> 0,257</td><td> 0,257</td><td> 0,266</td><td> 0,256</td><td> 0,246</td><td> 0,260</td>

<td>CoO (ppm)</td><td> 134</td><td> 129</td><td> 131</td><td> 128</td><td> 126</td><td> 128</td><td> 127</td><td> 126</td><td> 116</td><td> 126</td>

<td>Se (ppm)</td><td> 11</td><td> 10</td><td> 11</td><td> 11</td><td> 6</td><td> 7</td><td> 5</td><td> 6</td><td> 8</td><td> 6</td>

<td>TiO₂ (% by weight)</td><td> 0,199</td><td> 0,188</td><td> 0,188</td><td> 0,173</td><td> 0,020</td><td> 0,021</td><td> 0,020</td><td> 0,021</td><td> 0,022</td><td> 0,020</td>

<td>LTA (%)</td><td> 28,1</td><td> 28,8</td><td> 29,5</td><td> 29,6</td><td> 35,1</td><td> 35,2</td><td> 35,4</td><td> 35,4</td><td> 35,7</td><td> 35, 8</td>

<td>TSUV (%)</td><td> 16, 6</td><td> 17,0</td><td> 18, 1</td><td> 19,1</td><td> 21,7</td><td> 21,4</td><td> 22,0</td><td> 21, 6</td><td> 20,4</td><td> 22, 12</td>

<td>TSIR (%)</td><td> 9,2</td><td> 9,2</td><td> 8,9</td><td> 9,7</td><td> 12,7</td><td> 13,9</td><td> 11/9</td><td> 12,7</td><td> 13,7</td><td> 12,4</td>

<td>TSET (%)</td><td> 18,0</td><td> 18,4</td><td> 18,6</td><td> 19,1</td><td> 24,5</td><td> 25,2</td><td> 24,3</td><td> 24,7</td><td> 25,1</td><td> 24, 8</td>

<td>DW (nm)</td><td> 488,6</td><td> 488,5</td><td> 487,7</td><td> 488,0</td><td> 484,9</td><td> 485,1</td><td> 484,7</td><td> 485,0</td><td> 487,0</td><td> 484,7</td>

<td>Pe (%)</td><td> 9,8</td><td> 10,0</td><td> 11,1</td><td> 9,5</td><td> 13,0</td><td> 12,0</td><td> 14,4</td><td> 13,2</td><td> 8,9</td><td> 13,7</td>

190 730 cd. table 1

<td></td><td>Ex. 11</td><td>Ex. 12 comp.</td><td>Ex. 13</td><td>Ex. 14</td><td>Ex. 15</td><td>Ex. 16</td><td>Ex. 17</td><td>Ex. 18</td><td>Ex. 19</td>

<td>Total iron (% by weight)</td><td> 1234</td><td> 1225</td><td> 1,226</td><td> 1204</td><td> 1212</td><td> 1217</td><td> 1208</td><td> 1213</td><td> 1204</td>

<td>FeO (% by weight)</td><td> 0,313</td><td> 0,296</td><td> 0,318</td><td> 0,384</td><td> 0,325</td><td> 0,323</td><td> 0,315</td><td> 0,312</td><td> 0,307</td>

<td>Redox model.</td><td> 0,254</td><td> 0,242</td><td> 0,259</td><td> 0,319</td><td> 0,268</td><td> 0,265</td><td> 0,261</td><td> 0,257</td><td> 0,255</td>

<td>CoO (ppm)</td><td> 126</td><td> 124</td><td> 126</td><td> 91</td><td> 93</td><td> 92</td><td> 94</td><td> 94</td><td> 90</td>

<td>Se (ppm)</td><td> 5</td><td> 6</td><td> 6</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>

<td>TiO2 (wt%)</td><td> 0,022</td><td> 0,019</td><td> 0,020</td><td> 0,024</td><td> 0,029</td><td> 0,032</td><td> 0,032</td><td> 0,032</td><td> 0,028</td>

<td>LTA (%)</td><td> 36,2</td><td> 36,3</td><td> 36,4</td><td> 44,7</td><td> 45,4</td><td> 45,4</td><td> 45,5</td><td> 45,6</td><td> 46,7</td>

<td>TSUV (%)</td><td> 22,3</td><td> 21,7</td><td> 22,5</td><td> 29,3</td><td> 27,7</td><td> 27,4</td><td> 27,3</td><td> 27,2</td><td> 27,8</td>

<td>TSIR (%)</td><td> 12,9</td><td> 14,3</td><td> 12,7</td><td> 8,5</td><td> 11,9</td><td> 12,3</td><td> 12,8</td><td> 13,0</td><td> 13,3</td>

<td>TSET (%)</td><td> 25,2</td><td> 26,0</td><td> 25,2</td><td> 26,9</td><td> 29,0</td><td> 29,1</td><td> 29,5</td><td> 29,7</td><td> 30,3</td>

<td>DW (nm)</td><td> 484,7</td><td> 485,0</td><td> 484,6</td><td> 484,8</td><td> 484,9</td><td> 484,9</td><td> 494,9</td><td> 484,0</td><td> 485,2</td>

<td>Pe (%)</td><td> 13,8</td><td> 12,8</td><td> 14,3</td><td> 18,0</td><td> 17,0</td><td> 16, 9</td><td> 16,5</td><td> 16,7</td><td> 16,1</td>

Table 2

<td></td><td>Ex.20 compare</td><td>Ex. 21 comp.</td><td>Ex. 22 comp.</td><td>Ex. 23 comp.</td><td>Ex. 24</td><td>Ex. 25</td><td>Ex. 26</td><td>Ex. 27 compare</td><td>Ex. 28</td>

<td>Total iron (% by weight)</td><td> 1,8</td><td> 1,8</td><td> 1,6</td><td> 145</td><td> 1.3</td><td> 0,975</td><td> 1,1</td><td> 1,1</td><td> 1,1</td>

<td>FeO (% by weight)</td><td> 0,63</td><td> 0,63</td><td> 0,56</td><td> 0,51</td><td> 0,46</td><td> 0,23</td><td> 0,17</td><td> 0,17</td><td> 0,33</td>

<td>Redox model.</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,35</td><td> 0,24</td><td> 0,15</td><td> 0,15</td><td> 0,3</td>

<td>CoO (ppm)</td><td> 200</td><td> 200</td><td> 175</td><td> 150</td><td> 140</td><td> 190</td><td> 200</td><td> 200</td><td> 110</td>

<td>Se (ppm)</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 10</td>

<td>TiO₂ (% by weight)</td><td> 0,6</td><td> 0</td><td> 0,6</td><td> 0,6</td><td> 0,4</td><td> 0,1</td><td> 0,05</td><td> 0</td><td> 0,02</td>

<td>LTA (%)</td><td> 23,9</td><td> 24,8</td><td> 27,8</td><td> 31,8</td><td> 34,9</td><td> 35,0</td><td> 35,0</td><td> 35,1</td><td> 35,5</td>

<td>TSUV (%)</td><td> 17,4</td><td> 21,5</td><td> 19,7</td><td> 21,7</td><td> 25,5</td><td> 30,8</td><td> 25,4</td><td> 25,9</td><td> 24,2</td>

<td>TSIR (%)</td><td> 2,7</td><td> 2,7</td><td> 2,8</td><td> 4,9</td><td> 6,5</td><td> 21,8</td><td> 32,7</td><td> 32,7</td><td> 12,7</td>

<td>TSET (%)</td><td> 14,1</td><td> 15,2</td><td> 16,3</td><td> 18,6</td><td> 21,1</td><td> 30,7</td><td> 36,0</td><td> 36,1</td><td> 23,6</td>

<td>DW (nm)</td><td> 482,1</td><td> 481,1</td><td> 482,7</td><td> 483,4</td><td> 483,0</td><td> 480,1</td><td> 480,6</td><td> 480,5</td><td> 485,2</td>

<td>Pe (%)</td><td> 34,5</td><td> 38,4</td><td> 30,5</td><td> 26,6</td><td> 25,9</td><td> 27,9</td><td> 24,9</td><td> 25,2</td><td> 9,9</td>

190 730

cd of table 2

<td></td><td>Ex. 29</td><td>Ex. thirty</td><td>Ex. 31</td><td>Ex. 32 compare</td><td>Ex. 33</td><td>Ex. 34</td><td>Ex. 35</td><td>Ex. 36</td><td>Ex. 37</td>

<td>Total iron (% by weight)</td><td> 1,0</td><td> 1,45</td><td> 1.1</td><td> 1,2</td><td> 1,1</td><td> 1,6</td><td> 1,3</td><td> 18</td><td> 1,1</td>

<td>FeO (% by weight)</td><td> 0,22</td><td> 0,32</td><td> 0,31</td><td> 0,31</td><td> 0,39</td><td> 0,35</td><td> 0,29</td><td> 0,40</td><td> 0,24</td>

<td>Redox model.</td><td> 0,22</td><td> 0,22</td><td> 0,28</td><td> 0,26</td><td> 0,35</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td>

<td>CoO (ppm)</td><td> 175</td><td> 140</td><td> 110</td><td> 150</td><td> 95</td><td> 140</td><td> 140</td><td> 110</td><td> 140</td>

<td>Se (ppm)</td><td> 1</td><td> 3</td><td> 10</td><td> 1</td><td> 10</td><td> 1</td><td> 3</td><td> 1</td><td> 3</td>

<td>TiO2 (^^,waj ^^ 'wo)</td><td> 0,4</td><td> 0,02</td><td> 0,02</td><td> 0,6</td><td> 0,02</td><td> 0,02</td><td> 0,02</td><td> 0,02</td><td> 0,02</td>

<td>LTA (%)</td><td> 35,9</td><td> 35,9</td><td> 36,0</td><td> 36,6</td><td> 36,1</td><td> 36,1</td><td> 37,1</td><td> 38,5</td><td> 38,9</td>

<td>TSUV (%)</td><td> 25,8</td><td> 20,0</td><td> 23,6</td><td> 21,8</td><td> 25,9</td><td> 18,8</td><td> 22,4</td><td> 16,3</td><td> 26,1</td>

<td>TSIR (%)</td><td> 23,7</td><td> 13,5</td><td> 14,4</td><td> 14,1</td><td> 9,4</td><td> 11,3</td><td> 16,3</td><td> 8,9</td><td> 20,9</td>

<td>TSET '(%)</td><td> 31,1</td><td> 24,6</td><td> 24,6</td><td> 25,2</td><td> 22,0</td><td> 23,5</td><td> 26,9</td><td> 22,5</td><td> 30,5</td>

<td>DW (nm)</td><td> 481,5</td><td> 485,0</td><td> 485,7</td><td> 484,0</td><td> 485,5</td><td> 485,3</td><td> 484,1</td><td> 488,6</td><td> 482,9</td>

<td>Pe (%)</td><td> 21,7</td><td> 17,3</td><td> 8,7</td><td> 19,0</td><td> 10,6</td><td> 19,4</td><td> 17,3</td><td> 15,4</td><td> 17,4</td>

cd of table 2

<td></td><td>Ex. 38 comp.</td><td>Ex. 39</td><td>Ex. 40 comp.</td><td>Ex. 41</td><td>Ex. 42</td><td>Ex. 43</td><td>Ex. 44 comp.</td>

<td>Total iron (% by weight)</td><td> 1,1</td><td> 1/1</td><td> 1,1</td><td> 1,0</td><td> 1,0</td><td> 1,0</td><td> 1,0</td>

<td>FeO (% by weight)</td><td> 0,28</td><td> 0,31</td><td> 0,28</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,25</td>

<td>Redox model.</td><td> 0,25</td><td> 0,28</td><td> 0,25</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,25</td>

<td>CoO (ppm)</td><td> 140</td><td> 130</td><td> 110</td><td> 120</td><td> 110</td><td> 95</td><td> 90</td>

<td>Se (ppm)</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>

<td>TiO2 (wt%)</td><td> 0</td><td> 0,1</td><td> 0</td><td> 0,05</td><td> 0,02</td><td> 0,02</td><td> 0</td>

<td>LTA (%)</td><td> 40,6</td><td> 41,0</td><td> 45,3</td><td> 45,6</td><td> 47,4</td><td> 50,1</td><td> 50,1</td>

<td>TSUV (%)</td><td> 29,6</td><td> 29,6</td><td> 30,0</td><td> 30,3</td><td> 30,7</td><td> 30,7</td><td> 32,1</td>

<td>TSIR (%)</td><td> 17,4</td><td> 14,4</td><td> 17,4</td><td> 23,8</td><td> 23,9</td><td> 23,9</td><td> 20,1</td>

<td>TSET (%)</td><td> 30,0</td><td> 28,4</td><td> 31,5</td><td> 35,3</td><td> 36,0</td><td> 36,9</td><td> 34,9</td>

<td>DW (nm)</td><td> 482,4</td><td> 482,8</td><td> 484,0</td><td> 483,4</td><td> 483,0</td><td> 485,0</td><td> 484, 9</td>

<td>Pe (%)</td><td> 22,4</td><td> 21,9</td><td> 18,2</td><td> 17,6</td><td> 16,4</td><td> 14,3</td><td> 15,3</td>

190 730

With regard to Tables 1 and 4, in accordance with the present invention, a blue-tinted glass has been developed, which has the basic condition of a glass of soda lime-quartz, an addition of iron, cobalt and titanium and possibly selenium, as materials absorbing red and ultraviolet radiation, and as dyes. and it has light transmittance (LTA) higher than ZP% Oo 6P% and a color characterized by a predominant wavelength (denoted here DW) in the range of oO 08P Oo 089 nanometers (nm), preferably oO 08′4 Oo 087 nanometers, and excitation purity (Pe) at least 8%, preferably 0 1 P 0 3 P%, all of the above values ​​being measured at a thickness of P.16 P inches (0.06 mm). It is anticipated that the color of the glass may vary with the predominant wavelength resulting in the desired product.

The rheOox of the glass is kept in the range of P, 15 Oo P, OP, preferably P, 4P Oo P, 35, more preferably P, 40 Oo P, 3Z. The glass composition also has a TSUV of no more than 35%, preferably no more than 3P%; has a TSIR of not more than Z5%, preferably not more than 4p%, and has a TSET of not more than OP%, preferably not more than 35%.

In one particular embodiment, the glass composition comprises 0.10 to 4% by weight of total iron, preferably 0.10 to 1.0% by weight of total iron, more preferably 0.1 to 1.3% by weight of total iron; oO P, 15 Oo P, 65% by weight FeO, preferably oO P, 4 Oo P, 5% by weight FeO, more preferably oO P, 40 Oo P, OP% FeO; and oO 9P Oo 45P ppm CoO, preferably oO 1PP Oo 15P ppm CoO, more preferably oO11Po 10p ppm CoO. As previously discussed, the glass composition may also contain selenium, in particular oO POo 14 ppm Se, preferably oO POo 8 ppm Se. In one particular embodiment, the glass composition according to the invention comprises about 10 10 6 ppm Se. Likewise, the glass composition may also contain titanium, in particular 0 P, P 4 O P, P% by weight of TiO 4, preferably closer to the lower concentration. In one particular embodiment, the glass composition according to the invention comprises o0 P, P4 Oo P, 3P% by weight TiO4.

In one particular embodiment, the glass composition is selenium free and has an LTA of greater than 4P% 60%, preferably greater than 35% 55%. In another embodiment, the composition according to the invention does not contain selenium and contains less than 4 PPM CoO. In yet a further embodiment, the glass composition according to the invention has 0 14 ppm Se and has an LTA of greater than 35% O 6 P%, preferably 0 O P% O 55%.

The swelling properties of the glass are expected to change when the glass is exited and then after prolonged exposure to ultraviolet radiation, referred to simply as "solarization". In particular, it is appreciated that the lowering and solarization of the glass compositions described herein can reduce the LTA and TSIR by about 0.5% by 1%, reduce the TSUV by about 10% by 4%, and TSET by about 10% by 1.5%. As a result, in one embodiment of the invention, the glass has selected voiding properties that initially fall outside the desirable range discussed previously, but fall within the desirable ranges after tapping and solarization.

The glass produced by the fleet process, as disclosed herein, typically has pane thicknesses of 0 about 1 millimeter 0 1 P millimeters -.

When using O0 vehicle glazing, it is preferred that the glass panes having the composition and voiding properties described herein have a thickness of OO, 10 O P, 197 inches (0.1 to 5 mm). It is anticipated that when using a single layer of glass with the above thickness range, the glass, for example, on a side or rear window of a motor vehicle, will be tilted down.

It is also noted that glass can also be used in architecture and for use at thicknesses of about 0, 10 about 0.40 inch (about 3.6 about 6 mm).

When multiple layers are used in automotive or architecture applications, it is envisioned that the glass layers are stressed and laminated together using a thermoplastic adhesive such as pdivin and butyral.

As discussed previously, other materials may also be present in the glass compositions of the present invention to further reduce the transmission of red and ultraviolet radiation and optionally to adjust the color of the glass. Especially poO is taken

190 730 Note that the following materials may be added to the soda-lime-quartz glass described herein containing iron, cobalt, and titanium, and possibly selenium:

Nd2O3 from 0 to 1% by weight

SnO2 from 0 to 2% by weight

ZnO from 0 to 1% by weight

MoO3 from 0 to 003% by weight

CeO2 from 0 to 2% by weight

NiO from 0 to 0.1% by weight.

It should be obvious that adjustments have to be made to the basic iron, cobalt, selenium and titanium components which are responsible for the coloration and possibly the redox indicator influencing the strength of these additional materials.

As is known to those skilled in the art, other variants may also be used without departing from the scope of the invention as defined in the claims.