CZ20003359A3 - Bronze colored glass, sheet glass and window for automobile vehicle - Google Patents

Abstract

Infrared-absorbing bronze glass ultraviolet radiation as a constituent, contains SiO2 66 to 75 wt%, Na 2 O 10 to 20 wt%, CaO 5 to 15 wt%, MgO 0 to 5% by weight, Al2O3 0 to 5% by weight, and K2O 0 to 5 % by weight, and as solar radiation absorbing components a the ink supply comprises a total iron of 0.7 to 2.2% by weight, FeO 0.15 to 0.5 wt%, with 3 to 100 ppm, CoO 0 to 100 ppm, wherein the glass has a light transmittance (LTA) of up to 60% a characterized by a dominant wavelength in the range of 571 to 590 nanometers and coordinate purity 12 to 75% at a thickness of about 4.06 mm.

Description

Technical field

The invention relates to a bronze-colored soda-lime-silica glass having low light transmittance, which makes it desirable for use in vehicle privacy glass, such as in the side and rear windows of trucks or glass roofs of automotive vehicles. Bronze-colored is understood herein to include glasses having a dominant wavelength (equivalent wavelength in terms of the CIE color coordinate definition) of about 560 to 590 nm, and which may also be referred to as yellow-green, yellow-orange or yellow-gray. These glasses further require the use of lower transmittance for infrared or ultraviolet radiation as compared to typical bronze glasses for use in automotive vehicles, and compatibility with float manufacturing technology.

BACKGROUND OF THE INVENTION

Various compositions for dark colored glasses absorbing infrared and ultraviolet radiation are known. The primary colorant in a typically dark-colored automotive privacy glass is iron, which is usually present in both Fe ₂ O ₃ and FeO. Some glasses use cobalt, selenium and optionally nickel in combination with iron to further control ultraviolet radiation and color, such as disclosed in U.S. Pat. Nos. 4,873,206 (Jones), 5,278,108 (Cheng et al.), 5,393 593 (Baker et al.), 5

308,805 (Gulotta et al.), 5,545,596 and 5,582,455 (Casariego et al.) And in European patent application EP 0 705 800. Other solutions also include chrome with this combination of colors, such as U.S. Pat.

104,076 (Pons), 4,339,541 (Ruye Cannons), 5,023,210 (Krumwiede et al.) And 5,352,640 (Combes et al.), Or EP 0 536 049, FR 2,331,527 and CA 2,148,954. Glass according to U.S. Pat

521 128, 5 346 867 (Jones et al.) And 5 411 922 (Jones) further comprise manganese and / or titanium. Still other glasses may also contain other materials as described in WO 96/00194 which proposes to use fluorine, zirconium, zinc, cerium, titanium and copper in the composition of the glass, and requires that the sum of alkaline earth oxides be less than 10 % by weight of glass.

In the manufacture of infrared and ultraviolet absorbing glasses, the relative amounts of iron and other additives must be accurately monitored and controlled within the operating range to provide the desired color and spectral properties. It would be desirable to have dark bronze tinted glass which could be used as a privacy glass in vehicles for refilling bronze tinted glass, typically used in cars and trucks, which has a higher ability to block the passage of sunlight and which is compatible with commercially available float glass manufacturing methods.

SUMMARY OF THE INVENTION

The invention provides a bronze-colored infrared and ultraviolet absorbing glass having a light transmission of up to 60%. The glass uses a standard composition for soda-lime-silica glasses with an additional content of iron and selenium and possibly cobalt as absorbing materials. · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

-3 infrared and ultraviolet radiation and as dyes. The glass according to the invention has a light transmittance (LTA) of up to 60% and its color is characterized by a dominant (replacement) wavelength in the range of 560 to 590 nanometers and a coordinate purity (more precisely, coordinate purity expressed as a percentage, essentially saturation) of 12 to 75%. a thickness of 0.16 inches (approximately 4.06 mm).

In one embodiment of the invention, the glass for forming an infrared and ultraviolet absorbing bronze-colored soda-lime-silica glass product comprises an absorbing and coloring portion consisting essentially of 0.7 to 2.2 wt% total iron, 0.15 up to 0.5 wt% FeO, 3 to 100 ppm Se, and optionally up to 200 ppm CoO, and preferably 1.1 to 1.4 wt% total iron, 20 to 45 ppm Se and 0 to 70 ppm CoO.

The base glass part of the glass according to the invention, i.e. the main glass components without infrared or ultraviolet absorbing materials and / or dyes of the present invention, is conventional soda-lime-silica glass with the following components, in percent by weight:

Sio ₂ 66 to 75% Na ₂ O 10 to 20% CaO 5 to 15% MgO 0 to 5% ai ₂ o ₃ 0 to 5 k ₂ o 0 to 5

The weight percentages are based on the total weight of the final glass.

• · ······································································ · · · · · · · · · · · · · · · · · ·

Infrared and ultraviolet absorbing materials and dyes in the form of iron and selenium and optionally cobalt are added to the base glass according to the invention. Iron is expressed here in the form of Fe ₂ O ₃ and FeO, selenium is expressed in the form of elemental Se, and cobalt is expressed in the form of CoO. It should be noted that the glasses herein may contain small amounts of other materials, such as melting and refining aids, impurities or impurities. Further, it should be noted that in one embodiment of the invention, small amounts of additional materials may be included in the glass to improve the solar transmittance properties, as detailed below.

Iron oxides in the glass composition perform several functions. Fe ₂ O ₃ is a strong UV absorber and acts as a yellow dye in the glass. FeO is a strong infrared absorbent and is used in the glass as a blue dye. The total amount of iron present in the glasses herein is expressed in terms of Fe ₂ O ₃ content in accordance with standard analytical practice, but does not mean that all iron will necessarily be in the form of Fe ₂ O ₃ . Similarly, the iron content in the ferrous state is referred to as FeO, although it is not necessarily present in the glass as ferrous oxide. In order to reflect the relative amounts of ferrous and ferric forms of iron in glass compositions, 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 Fe ₂ O ₃ ). Unless otherwise stated herein, the term total iron or total iron content shall mean total iron content expressed as Fe ₂ O ₃ and the term FeO shall be:

means iron in the ferrous state, expressed as FeO.

Selenium is an ultraviolet absorbing dye that gives the soda-lime-silica glass a pink to brown color. Selenium can induce deliberate absorption of infrared radiation and its use tends to reduce redox. CoO acts as a blue dye in the glass and does not exhibit appreciable absorption properties in terms of absorption of infrared or ultraviolet radiation. In order to achieve the desired bronze-tinted glass, providing privacy and the desired spectral properties, a proper balance is required between the iron content, i.e. iron and iron oxide, selenium and cobalt.

The glass according to the invention can be melted and refined in a continuous melting process on an industrial scale and shaped into flat glass sheets of variable thickness by the float process in which the molten glass is carried on a bath of molten metal, usually tin. known in the art.

While it is preferred that the glass described herein be manufactured by a conventional continuous top-melting process, as is well known in the art, the glass may also be produced using multi-stage melting as described in Kunkle U.S. Pat. No. 4,381,934. et al., 4,792,536 (Pecoraro et al.) and 4,886,539 (Cerutti et al.). If desired, within the melting and / or forming stages of the glass manufacturing process, a mixing device for homogenizing the glass may be used to produce glass of the highest optical quality.

·· ··· · · · · · · · · · · · · · · · · · ·

-64 4 * 4444 4 4 44 4 «·« · ·· ··· ·· 4 ··

Depending on the type of melting operation, sulfur may be added to the soda-lime glass batch materials as a melting and fining aid. Conventionally manufactured glass may contain up to about 0.3 wt% SO ₃ . In glass containing iron and sulfur, the provision of reducing conditions can produce an amber color that reduces light transmittance as disclosed in U.S. Patent No. 4,792,536 to Pecoraro et al. However, it is believed that the reducing conditions required to produce this coloration in the float glass of the type herein are limited to approximately the first 20 micrometers of the lower surface of the glass in contact with the molten tin during the float operation, and to a lesser extent affect the exposed upper surface of the glass. Due to the low sulfur content and the limited area of glass in which coloration could occur, depending on the particular composition of the soda-lime-silica glass, the sulfur on these surfaces has no significant effect on the color of the glass or the spectral properties.

It should be noted that due to the shaping of the glass on the molten tin, as mentioned above, measurable amounts of tin oxide can migrate to the surface portions of the glass on the side that contacts the molten tin. Typically, the float glass has a SnO ₂ concentration of at least 0.05 to 2 wt% in approximately the first 25 micrometers below the surface of the glass that has been in contact with the tin. Typical background levels of SnO ₂ can be up to 30 parts per million (ppm). It is believed that high tin concentrations in approximately the first 10 angstroem of the glass surface supported by molten tin can slightly increase the reflectance of the glass surface. However, the overall impact on glass properties is minimal.

44 44

4 4 4 4 4 44

4 4 4 4 4

4,444 4 9 4 4 44 4

4 44 4 4 444 4 4 4 —Ί -

In the description, the term dominant wavelength is used in the literal Czech translation of the dominant name wavelength for better clarity of the text, while the term substitute wavelength in the sense of the Czech nomenclature of CIE is always given in brackets. In the claims, only the standardized term wavelength according to the Czech nomenclature according to IEC 50 (845), used for coordinate characterization of color, is used for this quantity.

DETAILED DESCRIPTION OF THE INVENTION

Table 1 summarizes examples of experimental glass melts having compositions implementing the principles of the invention. Similarly, Table 2 summarizes a series of computer modeled glasses incorporating the principles of the invention. The modeled compositions were created on the basis of a computer model of glass color and spectral properties developed by PPG Industries, Inc. Tables 1 and 2 show only iron, selenium and cobalt as components in the examples given. Analysis of the selected experimental melts suggests that the melts are most likely to contain up to about 15 ppm Cr ₂ O ₃ , up to about 40 ppm MnO ₂ , and up to about 0.024 wt% TiO ₂ . It is believed that Cr ₂ O ₃ , MnO ₂ and TiO ₂ are introduced into the glass melts as part of the cullet. The modeled compositions were further modeled to contain up to 9 ppm Cr ₂ O ₃ and about 0.025 wt% TiO ₂ . It is further contemplated that the glasses according to the invention produced by the conventional float process as mentioned above may contain these materials, but the levels of these materials are considered to be admixture levels which do not materially affect the color and spectral properties of the bronze-colored glass.

-8 according to the invention.

The spectral properties shown in Tables 1 and 2 are based on a reference thickness of 0.16 inches (approximately 4.06 mm). It will be appreciated that the spectral properties of the examples may be approximated to different thicknesses using the formulas set forth in U.S. Patent 4,792,536.

With respect to the transmittance values shown in Table 1, the light transmittance (LTA) is measured at the normal light type A according to C.I.E. with an observer of 2 ° in the wavelength range 380 to 770 nm. The color of the glass, characterized by surrogate (dominant) wavelength and coordinate purity, was measured under normalized light type C with an observer of 2 ° according to ASTM E308-90. Total UV transmittance (TSUV) was measured in the wavelength range 300-400 nm and total infrared transmittance (TSIR) was measured in the 720-2000 nm wavelength range. Transmittance values TSUV, TSIR, and TSET were calculated under direct sunlight with Parry Moon 2.0 air mass and were integrated using a trapezoidal rule as known in the art. The spectral properties shown in Table 2 are related to the same wavelength ranges and calculation methods.

The information given in Table 1 is based on experimental laboratory melts containing approximately the following batch components:

shards

239.74 g · · * * * * * * ,7 ,7 ,7 ,7 ,7 ,7 ,7 ,7 ,7 # # # # # #

sand 331.10 g soda 108.27 g limestone 28,14 g dolomite 79,80 g sodium sulfate 2.32 g Fe ₂ O ₃ (total Fe) as required Se as required ^Co 3 ° 4 as required

The amount of ingredients was adjusted to give a total weight of 700 g of glass. Reducing agents were added as needed to control the redox value. The shards used in the melt (which represented approximately 30% of the melt) contained 0.51 wt% total iron, 0.055 wt% TiO ₂ and 7 ppm Cr ₂ O ₃ . In preparing the melt, the components were weighed and mixed. A portion of the feedstock was then placed in a silica crucible and heated to 1343 ° C (2450 ° F). When the batch material melted, the remaining raw materials were added to the crucible and the crucible was kept at 1343 ° C (2450 ° F) for 30 minutes. The molten charge was then heated and held for 30 minutes at 1371 ° C (2500 ° F), for 30 minutes at 1399 ° C (2550 ° F) and for 1 hour at 1427 ° C (2600 ° C). F). Then, the glass was fritted in water, dried, and reheated at 1454 ° C (2650 ° C) in a platinum crucible for two hours. The molten glass was then poured from the crucible to form a plate and cooled. Samples were cut from the plate and ground and polished for analysis.

Chemical analysis of the glass composition (except for FeO) was performed using RIGAKU 3370 X-ray fluorescence spectra-10. Of the photophotometer. The spectral characteristics of glass were determined on chilled samples using a Perkin-Elmer Lambda 9 UV / VIS / NIR spectrophotometer prior to glass curing or prolonged exposure to ultraviolet radiation, which affect the spectral properties of the glass. FeO and redox content were determined using glass color and a spectral behavior computer model developed by PPG Industries Inc.

Based on the charge composition for experimental melting

The following approximate values have been calculated contents of basic oxides falling within the above basic glass composition: of that sieve ₂ 72.1 % by weight At ₂ 0 13.6 % by weight CaO 8.8 % by weight MgO 3.8 % by weight ai ₂ o ₃ 0.18 wt% to ₂ ° 0.057 wt% It is expected that basic oxide components of industrial

The soda-lime-milled glass based on the experimental melts described in Table 1 and the modeled compositions of Table 2 will be similar to those mentioned above.

TAB.l

Př.l Ex.2 Ex.3 Ex.4 Ex.5 Ex.6 Total iron (wt%) 1.55 1.24 1.24 1,22 1,23 1,22 FeO (wt%) 0.435 0.324 0.328 0.325 0.354 0.365 Model.redox 0.280 0.262 0.265 0.266 0.287 0.299

• 4 ·· 4 · 4 44 «4 44 ·« · * 4

4444 4 · 44 44 • 444444 4 44 44 4

444 * ·· • 4 44 44 444

Se (ppm) 44 45 49 40 34 28 CoO (ppm) 126 127 128 126 129 124 LTA (%) 13.76 17.39 18.21 19.70 20.06 22.11 TSUV (%) 4.27 6.57 7.07 8.32 9.47 11.23 TSIR (%) 6.42 11.81 11.81 11.74 10.18 9.51 TSET (%) 9.66 14.46 14.97 15.51 15.00 15.47 DW (nm) 579.4 580.3 580.2 578.5 578.0 572.8 Pe (%) 33.7 28.1 25.6 20.2 17.5 13.4

Total iron Př.7 Ex.8 Př.9 Ex.10 Př.ll Ex.12 (wt%) 1,22 1.20 1.26 1,23 1.20 1,25 FeO (wt%) 0.269 0.309 0.242 0.312 0.329 0.333 Model.redox 0.220 0.257 0.192 0.254 0.274 0.266 Se (ppm) 30 37 31 37 21 17 CoO (ppm) 123 17 65 0 32 35 LTA (%) 25.04 31.72 32.36 33.96 35.93 37.48 TSUV (%) 11.00 9.26 10.10 9.15 14.15 14.70 TSIR (%) 16.81 13.32 19.75 13.12 11.82 11.70 TSET (%) 20.91 20.28 24.90 20.97 21.89 22.57 DW (nm) 576.9 580.4 577.5 579.3 575.1 572.7 Pe (%) 13.0 36.6 22.0 35.8 18.9 15.5

Total iron Ex.13 Př.14 Př.15 Ex.16 Ex.17 Př.18 (wt%) 1.24 1.24 1,22 1.19 1,22 1.19 FeO (wt%) 0.267 0.290 0.316 0.297 0.330 0.318 Model.redox 0.215 0.234 0.258 0.250 0.271 0.267

** BB B B »9 • 9 9 9 9 ·

99 99

Se (ppm) 23 20 May 22nd 18 19 Dec 16 CoO (ppm) 35 35 0 34 0 0 LTA (%) 37.96 38.54 40.31 40.35 43.20 47.62 TSUV (%) 12.95 14.33 13.56 16.07 15.65 18.27 TSIR (%) 17.10 14.95 12.87 14.31 11.90 12.73 TSET (%) 25.67 24.82 23.73 25.41 24.58 27.24 DW (nm) 576.5 574.8 577.0 573.8 574.7 573.5 Pe (%) 21.2 17.7 26.0 15.7 20.7 17.4

TAB.2

Total iron Př.19 Ex. 20 May Ex. 21 Př.22 Př.23 Př.24 (wt%) 0.72 0.72 , 075 0.72 2.1 1.9 FeO (wt%) 0.202 0.202 0.298 0.202 0.557 0.504 Model.redox 0.280 0.280 0.397 0.280 0.265 0.265 Se (ppm) 61 52 93 52 24 24 CoO (ppm) 190 175 50 126 35 35 LTA (%) 10.74 13.21 13.64 16.70 26.52 28.29 TSUV (%) 5.43 6.78 3.98 6.83 4.52 5.43 TSIR (%) 24.60 24.69 14.09 24.87 3.41 4.51 TSET (%) 19.13 20.31 14.13 21.64 12.33 13.85 DW (nm) 589.5 588.9 590.0 586.9 570.1 571.3 Pe (%) 31.7 25.5 70.3 35.1 25.0 24.0

Př.25 Ex. 26 Ex. 27 Mar: Ex. 28 Ex. 29 Ex. 30 Total iron (wt%) 1.75 1.45 1.35 1.32 1.15 1.06 FeO (wt%) 0.464 0.384 0.348 0.350 0.305 0.281

4 44444 4

-1344 44 44 444

Model.redox 0.265 0.265 0.258 0.265 0.265 0.265 Se (ppm) 24 24 35 24 24 24 CoO (ppm) 35 35 0 35 35 35 LTA (%) 26.69 32.74 33.79 34.16 36.12 37.20 TSUV (%) 6.24 8.34 6.86 9.50 11.30 12.42 TSIR (%) 5.59 8.69 10.66 7.58 13.71 15.77 TSET (%) 15.19 18.52 19.46 20.32 23.10 24.81 DW (nm) 572.2 574.3 580.7 575.2 576.6 577.4 Pe (%) 23.4 21.9 41.4 21.3 20.5 20.1

Total iron Př.31 Ex. 3 2 Ex. 33 Př.34 Ex. 35 (wt%) 0.95 1,2 1,2 1.1 0.9 FeO (wt%) 0.252 0.462 0.434 0.284 0.293 Model.redox 0.265 0.385 0.362 0.258 0.325 Se (ppm) 24 18 18 20 May 18 CoO (ppm) 35 6 6 0 10 LTA (%) 38.58 40.33 41.12 46.28 55.34 TSUV (%) 13.97 17.44 16.74 12.67 26.07 TSIR (%) 18.75 5.67 6.62 15.56 14.80 SET (%) 27.17 20.01 20.85 27.74 32.54 DW (nm) 578.5 570.5 572.0 577.4 561.0 Pe (%) 14.0 12.9 14.6 26.2 6.0

How results from Tables 1 and 2, the invention provides bronze colored glass, having standard basic

soda-lime-silica composition, and additionally iron and selenium and optionally cobalt, as well as infrared and ultraviolet absorbing materials and dyes, the glass having

a light transmittance (LTA) of up to 60%, and a color characterized by a dominant (replacement) wavelength (DW) in the range of 560 to 590 nm and a coordinate purity (Pe, expressed as a percentage) of 12 to 75%. It is contemplated that the color of the glass may vary within the range of substitute (dominant) wavelengths to obtain the desired product. For example, when the dominant (replacement) wavelength approaches 560 bm, the color may appear yellow-green, while when the dominant (replacement) wavelength approaches 590 nm, the glass color may appear yellow-orange. In addition, when the coordinate clarity decreases, the glass may look grayer, while as the coordinate clarity increases, the color of the glass becomes more intense.

The redox ratio for these glasses is maintained in the range of 0.15 to 0.40, preferably 0.18 to 0.30, and most preferably 0.24 to 0.29. These glasses also have a transmittance TSUV of no more than about 40%, preferably no more than 35% and a transmittance of TSIR no more than 30%, preferably no more than 20%, and a transmittance of TSET no more than 40%, preferably more than than 35%.

In one particular embodiment, the glass comprises 0.7 to 2.2 wt.% Total iron, preferably 1 to 1.6 wt.% Total iron, and more preferably 1.1 to 1.4 wt.% Total iron. 15 to 0.5 wt% FeO, preferably 0.2 to 0.4 wt% FeO and most preferably 0.24 to 0.36 wt% FeO, and 3 to 100 ppm selenium, preferably 20 to 80 ppm selenium, and most preferably 15 to 40 ppm selenium. The glass has an LTA light transmission of up to 60% by weight and a color characterized by a dominant (replacement) wavelength of 571 to 590 nm, preferably 575 to 585 nm, and a coordinate purity of 12 to 75%, preferably 15 to 35%, at 4, 06 mm (0.16). As mentioned above, • • · ·

Cobalt, and more particularly 0 to less than 100 ppm CoO, preferably 0 to 70 ppm CoO, and most preferably 20 to 50 ppm Co, are also present in the glass.

Further embodiments of the invention are disclosed which combine the same infrared and ultraviolet absorbing materials and the colorants mentioned above to form glass having the desired color and spectral properties.

In one embodiment, the glass comprises 0.7 to 1.35 wt% total iron, 0.15 to 0.5 wt% FeO, 3 to 100 ppm Se, and 0 to less than 100 ppm CoO, and has a LTA 20 permeability up to 60% and a color characterized by a dominant (replacement) wavelength of 560 to 590 nm and a coordinate purity of 12 to 75%, at a thickness of about 4.06 mm (0.16).

According to another embodiment, the glass comprises 0.7 to 2.2 wt% total iron, 0.15 to 0.5 wt% FeO, 3 to 100 ppm Se, and 0 to less than 100 ppm CoO, and has a light transmission of LTA 20 to 60 and a color characterized by a dominant (replacement) wavelength of 560 to 590 nm and a coordinate purity of 12 to 75%, at a thickness of about 4.06 mm (0.16).

According to another embodiment, the glass comprises 0.7 to 2.2 wt% total iron, 0.15 to 0.5 wt% FeO, 3 to 100 ppm Se, and 0 to 200 ppm CoO, and has a light transmission of LTA to 60 % and a color characterized by a dominant (replacement) wavelength of 571 to 590 nm and a coordinate purity of 15 to 75%, at a thickness of approximately 4.06 mm (0.16).

According to another embodiment, the glass comprises 0.7 to 1.35 wt% total iron, 0.15 to 0.5 wt% FeO, 3 to 100 ppm Se, and 0 to 200 ppm CoO, and has a light transmission of LTA to 60% and a color characterized by a dominant (replacement) wavelength of 560 to 590 nm and a coordinate purity of 15 to 75%, at a thickness of approximately 4.06 mm (0.16).

According to another embodiment, the glass comprises 0.7 to 2.2 wt% total iron, 0.15 to 0.5 wt% FeO, 3 to 100 ppm Se, and 0 to 200 ppm CoO, and has a light transmission of LTA 20 to 60% and a color characterized by a dominant (replacement) wavelength of 560 to 590 nm and a coordinate purity of 15 to 75%, at a thickness of approximately 4.06 mm (0.16).

According to another embodiment, the glass comprises 0.7 to 1.35 wt% total iron, 0.15 to 0.5 wt% FeO, 3 to 100 ppm Se, and 0 to 200 ppm CoO, and has a light transmittance of LTA 20 to 60% and a color characterized by a dominant (replacement) wavelength of 571 to 590 nm and a coordinate purity of 15 to 75%, at a thickness of approximately 4,06 mm (0,16).

It is expected that the spectral properties of glass will change upon curing of the glass, as it does after prolonged exposure to ultraviolet radiation, commonly referred to as solarization. In particular, it is estimated that the toughening and solarization of the glasses described herein may reduce LTA and TSIR transmittance by about 0.5 to 1%, reduce TSUV by about 1 to 2% and TSET by about 1 to 1.5%. As a result, in one embodiment of the invention, the glass has selected spectral properties which initially fall outside the desired ranges described above but will fall within these desired ranges after curing and / or solarization.

The float glass described herein typically has a sheet thickness range of about 1 to 10 mm.

For vehicle glazing, it is preferred that the glasses having the composition and spectral properties described above have a thickness in the range of 3.2 to 5 mm (0.126 to 0.197). It is envisaged that when glass is used as a single layer, it will be tempered, for example in the case of a side or rear automotive window.

It is also possible for the glass to be used in architecture where it is intended to be used in a thickness range of about 3.6 mm to about 6 mm (0.14-0.24).

When using multiple layers for use in motor vehicles or in architecture, it is envisaged that the glass layers will be of chilled glass and bonded together to a stack using a thermoplastic adhesive such as polyvinyl butyral.

As mentioned above, other materials may also be added to the above glass compositions to further reduce the infrared and ultraviolet radiation transmittance and / or to control the color of the glass. In particular, the following materials may be added to the soda-lime-silica glass comprising iron and selenium and optionally cobalt described herein:

^ - ^Γ 2θ3 0 % to 0.009 wt. tío ₂ 0 up to 0.9% by weight ^At 2 ° 5 0 up to 0.12 wt.% MnO ₂ 0 up to 1% by weight Nd ₂ O ₃ 0 up to 1% by weight SnO ₂ 0 up to 2 wt.% ZnO 0 up to 1% by weight Mo0 ₃ 0 up to 0.03 wt.% CeO ₂ 0 up to 2 wt.% NiO 0 up to 0.1 wt.%

It should be noted that it is possible to adjust the content of the constituents of iron, cobalt, chromium and / or titanium with respect to the ability of these filler materials and to influence the coloration and / or redox.

Other variations are possible and will be apparent to those skilled in the art without departing from the scope of the invention as defined by the claims.

Claims (36)

PATENT CLAIMS 1. Bronze-colored infrared and ultraviolet absorbing glass having a composition comprising a base glass portion comprising: SiO ₂ 66 to 7 5 wt.% Na ₂ O 10 to 20 wt% CaO 5 to 15 wt% MgO 0 to 5 wt% ^a1 2 ° 3 0 to 5 wt% k ₂ o 0 to 5 wt% and an absorbent portion solar radiation and color supply, consisting essentially of 0.7 to 2.2% by weight of total iron FeO 0.15 to 0.5 wt.% With 3 to 100 ppm CoO 0 to less than 100 ppm wherein the glass has a light transmission (LTA) of up to 60% and the color is characterized by a replacement wavelength ranging from 571 to 590 nanometers and a coordinate purity of 12 to 75% at a thickness of approximately 4.06 mm. Glass according to claim 1, characterized in that the total iron concentration is from 1 to 1.6% by weight, the FeO concentration is from 0.20 to 0.40% by weight, and the Se concentration is from 15 to 80 ppm. Glass according to claim 2, characterized in that the CoO concentration is 0 to 70 ppm. · 9 · 9 «9» • • 9 «« -20 · · · 20 20 20 20 20 20 20 20 20 Glass according to claim 2, characterized in that the total iron concentration is from 1.1 to 1.4% by weight, the FeO concentration is 0.24 to 0.36% by weight, and the Se concentration is 20 to 45 ppm. Glass according to claim 4, characterized in that it has a light transmittance (LTA) of 15 to 55%, a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total transmittance Solar energy (TSET) of 40% or less, and the color of the glass is characterized by a replacement wavelength in the range of 575 to 585 nanometers and a coordinate purity of 15 to 35% at a thickness of approximately 4.06 mm. 6. The glass of claim 5 having a light transmission (LTA) of 25-50%, a total solar ultraviolet (TSUV) transmission of 35% or less, a total solar infrared transmission (TSIR) of 30% or less, and a total transmittance Solar energy (TSET) 35% or less. Glass according to claim 4, characterized in that the CoO concentration is 20 to 60 ppm. Glass according to claim 7, characterized in that it has a light transmittance (LTA) of 15 to 55%, a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total transmittance Solar energy (TSET) of 40% or less, and the color of the glass is characterized by a spare wavelength in the range of 575 to 585 nanometers and a coordinate purity of 21 to 9 * 9999 9 * · 9 9 • 9 · 9 9 99 9 · ·· 99 999 99 9 15 to 35% at a thickness of approximately 4.06 mm. 9. The glass of claim 1 having a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total solar energy transmittance (TSET) of 40% or less. The glass of claim 9 having a total solar ultraviolet transmittance (TSUV) of 35% or less, a total solar infrared transmittance (TSIR) of 30% or less, and a total solar energy transmittance (TSET) of 35% or less. Glass according to claim 1, characterized in that the color of the glass is characterized by a replacement wavelength in the range of 575 to 585 nanometers and a coordinate purity of 15 to 35%. The light transmittance glass of claim 1, (LTA) 15 to 55%. characterized by having pro The light transmittance glass of claim 12, characterized by (LTA) 25 to 45%. by having pro A flat glass sheet formed by the glass float process of claim 1. An automobile vehicle window formed from a flat glass pane according to claim 14. 16. Bronze-colored infrared absorbing glass • 1 4 4 9 19 4 9 4 4 4 5 4 4 995 4 4 · 4 9 4 9 5 14 4 4 4 4 5 -22a ultraviolet radiation having a composition comprising a base glass portion which comprises SÍO ₂ 66 to 75 % by weight Na ₂ O 10 to 20 May % by weight CaO 5 to 15 Dec % by weight MgO 0 to 5 % by weight ^A1 ° 2 0 to 5 % by weight to ₂ ° 0 to 5 % by weight and a solar absorbing and color delivery portion consisting essentially of a total iron of 0.7 to 1.35% by weight FeO 0.15 to 0.5 wt.% With 3 to 100 ppm CoO 0 to less than 100 ppm wherein the glass has a light transmission (LTA) of up to 60% and the color is characterized by a replacement wavelength ranging from 560 to 590 nanometers and a coordinate purity of 12 to 75% at a thickness of approximately 4.06 mm. Glass according to claim 16, characterized in that the glass has a light transmittance (LTA) of 15 to 55%, a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total solar energy transmittance (TSET) 40% or less, and the color of the glass is characterized by a replacement wavelength in the range of 570-585 nanometers and a coordinate purity of 15-35% at a thickness of approximately 4.06 mm. -23 ·· * · · · · · · · · · · · · · · · · · · · · 18. Bronze-colored infrared and ultraviolet absorbing glass having a composition comprising a base-glass part comprising: SiO ₂ 66 to 75 wt. At ₂ 0 10 to 20 May wt. CaO 5 to 15 Dec wt. MgO 0 to 5 wt. ^a1 2 ° 3 0 to 5 wt. k ₂ o 0 to 5 wt. and a solar absorbing and color delivery portion consisting essentially of total iron of 0.7 to 2.2 wt% FeO 0.15 to 0.5 wt.% With 3 to 100 ppm CoO 0 to less than 100 ppm wherein the glass has a light transmission (LTA) of up to 20 to 60% and the color is characterized by a replacement wavelength ranging from 560 to 590 nanometers and a coordinate purity of 12 to 75% at a thickness of approximately 4.06 mm. Glass according to claim 18, characterized in that the glass has a light transmission (LTA) of 25 to 40%, a total solar ultraviolet (TSUV) transmission of 40% or less, a total solar infrared transmission (TSIR) of 35% or less, and a total solar energy transmittance (TSET) 40% or less, and the color of the glass is characterized by a replacement wavelength in the range of 570-585 nanometers and a coordinate purity of 15-35% at a thickness of approximately 4.06 mm. • 4 444 -24444 20. Bronze tinted glass, absorbing infrared and ultraviolet radiation, having a composition comprising a base glass part, comprising Si ° ₂ 66 to 75 % by weight Na ₂ O 10 to 20 May % by weight CaO 5 to 15 Dec % by weight MgO 0 to 5 % by weight ai ₂ o ₃ 0 to 5 % by weight to ₂ ° 0 to 5 % by weight and a solar absorbing and color delivery portion consisting essentially of total iron of 0.7 to 2.2 wt% FeO 0.15 to 0.5 wt.% With 3 to 100 ppm CoO 0 to 200 ppm wherein the glass has a light transmission (LTA) of up to 60% and the color is characterized by a replacement wavelength in the range of 571 to 590 nanometers and a coordinate purity of 15 to 75% at a thickness of approximately 4.06 mm. Glass according to claim 20, characterized in that the glass has a light transmittance (LTA) of 15 to 55%, a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total solar energy transmittance (TSET) 40% or less, and the color of the glass is characterized by a replacement wavelength in the range of 575 to 585 nanometers and a coordinate purity of 15 to 35% at a thickness of approximately 4.06 -2544 44 4 · 4 4 ·· ♦ 4 45 4 4 4 4 · 4 4 • 4 · 4 4 4 · · · 44 44 44 4 44 mm. 22. Bronze-colored infrared and ultraviolet absorbing glass having a composition comprising a vitreous element comprising: SÍO ₂ 66 to 75 % by weight Na ₂ O 10 to 20 May % by weight CaO 5 to 15 Dec % by weight MgO 0 to 5 % by weight Al 2θ3 0 to 5 % by weight κ ₂ ο 0 to 5 % by weight and a solar absorbing and color delivery portion consisting essentially of a total iron of 0.7 to 1.35% by weight FeO 0.15 to 0.5 wt.% With 3 to 100 ppm CoO 0 to 200 ppm wherein the glass has a light transmission (LTA) of up to 60% and the color is characterized by a replacement wavelength ranging from 560 to 590 nanometers and a coordinate purity of 15 to 75% at a thickness of approximately 4.06 mm. Glass according to claim 22, characterized in that it has a light transmittance (LTA) of 15 to 55%, a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total transmittance Solar energy (TSET) of 40% or less, and the color of the glass is characterized by a spare wavelength in the range of 570 to 585 nanometers and coordinate-9 · 9 9 9 999 9 99 9 9 999 999 9 99 9900 99 99 99 99 999 99 9 with a purity of 15 to 35% at a thickness of approximately 4.06 mm. 24. Bronze-colored infrared and ultraviolet absorbing glass having a composition comprising a base-glass part comprising: SiO ₂ 66 to 75 % by weight At ₂ 0 10 to 20 May % by weight CaO 5 to 15 Dec % by weight MgO 0 to 5 % by weight ^A1 ° 2 0 to 5 % by weight to ₂ ° 0 to 5 % by weight and a solar absorbing and color delivery portion consisting essentially of total iron of 0.7 to 2.2 wt% FeO 0.15 to 0.5 wt.% With 3 to 100 ppm CoO 0 to 200 ppm wherein the glass has a light transmission (LTA) of up to 20 to 60% and the color is characterized by a replacement wavelength in the range of 560 to 590 nanometers and a coordinate purity of 15 to 75% at a thickness of approximately 4.06 mm. The glass of claim 24 having a light transmittance (LTA) of 25 to 40%, a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total transmittance Solar energy (TSET) of 40% or less, and the color of the glass is characterized by a spare wavelength in the range of 570 to 585 nanometers and a co-ordinate * 9 9 9 9 4 4 9 4 9 5 44 94 94 -274 at a purity of 15 to 35% at a thickness of about 4.06 mm. 26. Bronze-colored glass absorbing infrared and ultraviolet radiation, having a composition comprising a glass element containing: SiO ₂ 66 to 75 % by weight Na ₂ O 10 to 20 May % by weight CaO 5 to 15 Dec % by weight MgO 0 to 5 % by weight Al 2Ο3 0 to 5 % by weight K ₂ o 0 to 5 % by weight and a solar absorbing and color delivery portion consisting essentially of a total iron of 0.7 to 1.35% by weight FeO 0.15 to 0.5 wt.% With 3 to 100 ppm CoO 0 to 100 ppm wherein the glass has a light transmission (LTA) of up to 20 to 60% and the color is characterized by a replacement wavelength ranging from 571 to 590 nanometers and a coordinate purity of 15 to 75% at a thickness of approximately 4.06 mm. The glass of claim 26 having a light transmittance (LTA) of 25-40%, a total solar transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total transmittance Solar energy (TSET) of 40% or less, and the color of the glass is characterized by a replacement wavelength in the range of 575 to 585 nanometers and a coordinate of 9 9 9 9 9,999 9 9 9 9 9 9 · · 9 9 9 · 9 9 9 9 9 9 99 9 -2899 with a purity of 15 to 35% at a thickness of about 4.06 mm. 28. Bronze-colored infrared and ultraviolet absorbing glass having a composition comprising a base-glass element containing: Si0 ₂ 66 to 75 % by weight At ₂ 0 10 to 20 May % by weight CaO 5 to 15 Dec % by weight MgO 0 to 5 % by weight ^A1 ° 2 0 to 5 % by weight k ₂ o 0 to 5 % by weight and a solar absorbing and color delivery portion consisting essentially of total iron of 0.7 to 2.2 wt% FeO 0.15 to 0.5 wt.% Se 3 to 100 ppm CoO 0 to less than 100 ppm ^Cr 2 ° 3 0 to 90 ppm tío ₂ 0 to 0.9 wt.% ^At 2 ° 5 0 to 0.12 wt.% MnO ₂ 0 to 1 wt.% Nd ₂ O ₃ 0 to 1 wt.% SnO ₂ 0 to 2 wt.% ZnO 0 to 1 wt.% Mo0 ₃ 0 to 0.03 wt% CeO ₂ 0 to 2 wt NiO 0 to 0.1 wt.% wherein the glass has a light transmission (LTA) of up to 60% and the color is • BB B BB Β B · • ♦ B (B) • Β B (B) • B Β B • • Β Β B « B · « • Β B • • Β B (B) (B) (B) (B) (B) BB BB BB BBB Β Β B characterized by a replacement wavelength in the range of 571 to 590 nanometers and a coordinate purity of 15 to 75% at a thickness of approximately 4.06 mm. The glass of claim 28 having a total solar ultraviolet transmittance (TSUV) of 40% or less, a total solar infrared transmittance (TSIR) of 35% or less, and a total solar energy transmittance (TSET) of 40% or less. Glass according to claim 28, characterized in that the color of the glass is characterized by a replacement wavelength in the range of 575 to 585 nanometers and a coordinate purity of 15 to 35%. Glass according to claim 28, characterized in that it has a total solar transmittance (TSUV) of 35% or less, a total solar infrared transmittance (TSIR) of 30% or less and a total solar energy transmittance (TSET) of 35% or less, wherein the color of the glass is characterized by a replacement wavelength in the range of 575 to 585 nanometers and a coordinate purity of 15 to 35%. Glass according to claim 31, characterized in that the total iron concentration is from 1.0 to 1.6% by weight, the FeO concentration is from 0.20 to 0.40% by weight, and the Se concentration is from 15 to 80% by weight. ppm. The glass according to claim 22, wherein the CoO concentration is 0 to 70 ppm. 34. Float glass sheet formed by the float process # # # # # # · ·· ·· A glass according to claim 28. 35. Bronze tinted glass absorbing infrared and ultraviolet radiation, having a composition comprising a base glass part comprising: Si0 ₂ 66 to 75 % by weight Na ₂ O 10 to 20 May % by weight CaO 5 to 15 Dec % by weight MgO 0 to 5 % by weight ai ₂ o ₃ 0 to 5 % by weight k ₂ o 0 to 5 % by weight and a solar absorbing and color delivery portion consisting essentially of total iron of 0.7 to 2.2 wt% FeO 0.15 % to 0.5 wt Se 3 to 100 ppm CoO 0 to 200 ppm ^Cr 2 ° 3 0 to 90 ppm tío ₂ 0 to 0.9 wt% ^At 2 ° 5 0 to 0.12 wt% MnO ₂ 0 to 1 wt% Nd ₂ ° 3 0 to 1 wt% SnO ₂ 0 to 2 wt% Z nO 0 to 1 wt% Mo0 ₃ 0 to 0.03 wt% CeO ₂ 0 to 2 wt% and NiO 0 to 0.1 wt% wherein the glass has a light transmission (LTA) of up to 60% and the color is -31 · · · 9 9 9 9 9 9 t t t t t t t t t t Characterized by a replacement wavelength in the range of 571 to 590 nanometers and a coordinate purity of 15 to 75% at a thickness of approximately 4.06 mm. Glass according to claim 35, characterized in that it has a total solar transmittance (TSUV) of 35% or less, a total solar infrared transmittance (TSIR) of 30% or less and a total solar energy transmittance (TSET) of 35% or less, and the color is characterized by a replacement wavelength in the range of 575 to 585 nanometers and a coordinate purity of 15 to 35%.