|Publication number||USRE37998 E1|
|Application number||US 08/720,370|
|Publication date||Feb 18, 2003|
|Filing date||Sep 27, 1996|
|Priority date||Apr 13, 1990|
|Also published as||CA2039959A1, CA2039959C, DE69122798D1, DE69122798T2, EP0452207A1, EP0452207B1, US5352640|
|Publication number||08720370, 720370, US RE37998 E1, US RE37998E1, US-E1-RE37998, USRE37998 E1, USRE37998E1|
|Inventors||Pierre Combes, Jean-Jacques Massol, Pedro Casariego Alvarez|
|Original Assignee||Saint-Gobain Vitrage|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (48), Non-Patent Citations (3), Referenced by (3), Classifications (25), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation of application Ser. No. 07/682,497, filed Apr. 9, 1991, now abandoned.
The present invention relates to glass compositions used in the production of colored glazings, particularly for motor vehicle sunroofs.
Now, more than ever before, automobile designers are incorporating into their designs glazings formed of colored glass which have both a functional purpose and an attractive appearance. This tendency is confirmed by the ever increasing glazed surface of new automobile models compared with older types.
As a result, the greenhouse effect is an important factor which must be taken into account in determining the air conditioning requirements for such automobiles. This is more particularly true in the case of cars equipped with glass sunroofs. In an attempt to reduce this greenhouse effect, numerous unsuccessful attempts have previously been made by those skilled in the art to produce colored glass compositions having the low light and energy transmission properties offered by the glasses of the present invention.
The present invention is directed to glass compositions which are highly colored, particularly grey-blue or green glasses, which are suitable for the applications described above. For a given thickness, these glasses have a very low total light transmission and total energy transmission.
According to the invention, these attributes are obtained with the use of a colored glass formulation comprising the following constituents in the weight proportions defined by the following limits:
64 to 75%
0 to 5%
0 to 5%
5 to 15%
0 to 5%
10 to 18%
0 to 5%
wherein the total amount of the alkaline earth oxides ranges between 6 and 16% by weight and further wherein the total amount of alkali metal oxides is between 10 and 20% by weight. At least one of Al2O3, B203, MgO or K2O, each in an amount of up to 5% (0.05) by weight, therefore may be employed. The glass compositions of the invention also incorporate, as coloring agents:
Fe2O3 (total iron)
1.4 to 4%
0 to 0.05%.
The amount of CoO is preferably greater than about 0.02% by weight when the amount of Fe2O3 is less than about 2% by weight. Optionally, selenium and/or chromium oxide may also be added to the glass composition to provide additional coloration. The sum of CoO+selenium+Cr2O3 is preferably no greater than 0.24. The glass of the invention has a total light transmission factor under illuminant A (i.e., designated as “TLA”) less than or equal to about 20% and a total energy transmission factor (i.e., “TE”) equal to or below approximately 12% at a “standard” glass thickness of 3.85 mm.
Glazings formed with the glasses produced according to the invention are produced under conditions such that their redox potential, i.e., defined as the ratio of the ferrous oxide to the total quantity of iron, both expressed in the form of ferric oxide, ranges between about 0.16 and 0.40. Most of the glasses according to the invention, i.e., at least those having an iron content equal to or above approximately 2%, are produced in electric furnaces. The remaining compositions are compatible with conventional reverberatory furnaces.
For a given thickness, the colored glasses according to the invention preferably have a total light transmission below about 15%, or more preferably below 12%. The total energy transmission of these glasses is generally below about 8%.
In order to obtain the desired optical characteristics, particularly the aforementioned light and energy transmission values, the percentage of the coloring agents in the glass is adjusted, depending upon the thickness of the glass.
Thus, for a thickness of 3.85 millimeters, the colored glasses formed according to the invention can incorporate iron oxide as the sole coloring agent when the total content of this material, expressed as Fe2O3, is greater than about 3%. For such glasses, the production conditions are controlled in a manner known to those in the art such that their redox potential remains preferably equal to or below 0.30. The dominant wavelength of the glass thus obtained, when illuminated under illuminant C, is between about 500 and 570 nanometers.
For the same thickness, colored glasses produced according to the invention having a total iron oxide content (expressed as Fe2O3) equal to or below about 3%, may further comprise cobalt oxide as an additional coloring agent.
Thus, in one embodiment of the invention, the colored glass comprises between about 2 and 3% Fe2O3, approximately 140 to 400 ppm of CoO and optionally up to 50 ppm of selenium.
In general, such glasses have a dominant wavelength under illuminant C of between about 485 and 505 nm. Their total energy transmission factor is equal to or below approximately 10% and is generally between 4 and 6.5%. The excitation purity of these glasses under illuminant C is generally below about 30%. The glasses of the invention, which have a particularly low total light transmission factor, can have a relatively high excitation purity without having an excessively detrimental action on the visual perception of the color neutrality of the glass.
In a further embodiment of the invention, the glass compositions may optionally have a lower content of cobalt oxide and selenium in accordance with the following weight proportions:
1.4 to 2.5%
150 to 330 ppm
10 to 35 ppm
When illuminated under illuminant C, these glasses have a dominant wavelength between about 485 and 570 nm and their excitation purity is generally below 20%. Their total energy transmission factor is below 10% and is usually between 5 and 8%. Glasses with a dominant wavelength between 485 and 500 nm are preferred for aesthetic reasons.
For a thickness of 3.85 mm the colored glasses formed according to the invention with a total iron oxide content, expressed as Fe2O3, equal to or below about 2.5%, can incorporate cobalt oxide and chromium oxide.
Thus, in another embodiment of the invention, the colored glass may comprise between about 1.5 and 2.5% Fe2O3, between about 150 and 300 ppm of cobalt oxide and between 700 and 2000 ppm of chromium oxide. When illuminated under illuminant C, these glasses have a dominant wavelength between about 490 and 510 nm and an excitation purity of about 10 to 25%. Their total energy transmission factor is below 10% and in general between about 5 and 8%.
To form the glasses according to the invention, the basic composition used is conventional in the float glass industry. Coloring agents are added to the composition in sufficient proportions to make it possible, for a given thickness, to obtain the desired optical characteristics and appearance. The basic glass has the following formulation (in percent by weight):
The coloring agents are added to the glass in place of a portion of the silica.
The various examples appearing in Tables I and II set forth below illustrate different combinations of coloring agents. The values for the optical characteristics indicated were measured on 3.85 mm thick glazings. These glasses were formed under conditions such that they have a redox potential preferably equal to or below 0.35.
For glasses containing iron and cobalt oxide as coloring agents and having between approximately 2 and 3% of iron, it is desirable to include at least about 140 ppm of CoO within a 3.85 mm thick glazing. At lower amounts of CoO, the light transmission of the glass tends to increase and can exceed 15%.
For glasses colored with selenium and iron and cobalt oxides, it is recommended to introduce at least 1.4% iron oxide for a 3.85 mm thick glazing. Below this percentage, the light and energy transmissions of the glass respectively exceed 15 and 12%.
The glass compositions set forth in Tables I and II below and the preceding remarks concerning certain combinations of coloring agents are provided only to illustrate the numerous variations which can be produced without passing outside the scope of the invention and are not meant to limit the invention in any manner.
The glass formulations of the invention are compatible for use with standard prior art procedures for producing float glass, provided that certain glasses, i.e., those having an iron content greater than or equal to about 2%, are produced in electrical furnaces. The thickness of the ribbon of glass obtained in the float glass process, e.g., by layering the molten glass on a tin bath, can vary between 2 and 10 mm and preferably between 3 and 6 mm, where the glass is intended for the production of a glazing for a sunroof.
Glazings obtained by cutting a ribbon of colored glass formed according to the present invention, optionally followed by bending to a desired shape, may be used directly for producing a sunroof for a car in such a way as to reconcile the aesthetic requirements with the requirements concerning passenger comfort
As known in the art, such glazings may initially be surface treated or they may be combined with, e.g., a sheet of uncolored glass, an organic coating such as a polyurethane-based film with anti-lacerating properties, or a film ensuring a tight seal in the case of breakage. These glazings may also be locally coated with, e.g., an enamel coating.
Furthermore, glazings formed according to the invention can additionally be coated with at least one metal oxide layer such as tin oxide, obtained by a high temperature chemical deposition technique such as pyrolysis, e.g. in accordance with the process described in U.S. Pat. No. 4,500,567, which discloses thermally decomposing an organic tin compound, the disclosure of which is incorporated herein by reference or chemical vapor deposition (CVD) or by vacuum deposition, which processes are well known in the art. In the case of a glazing for use in forming the sunroof of a car, the metal oxide coating makes it possible to further improve the light and energy transmission properties of the glass.
Coloring Agents (% by weight)
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|US2418684||May 23, 1945||Apr 8, 1947||Du Pont||Selenium ruby glass|
|US2524719||Nov 26, 1946||Oct 3, 1950||American Optical Corp||Glass composition|
|US2860059||Sep 3, 1953||Nov 11, 1958||Libbey Owens Ford Glass Co||Ultra-violet light absorbing glass|
|US2892726||Oct 28, 1955||Jun 30, 1959||Pittsburgh Plate Glass Co||Glass composition|
|US2938808||Feb 25, 1957||May 31, 1960||Pittsburgh Plate Glass Co||Glass composition|
|US3291585||Apr 16, 1963||Dec 13, 1966||Asahi Glass Co Ltd||Method for the treatment of raw glass material containing easily volatilizable ingredients|
|US3294556||Jul 19, 1963||Dec 27, 1966||Corning Glass Works||Tan ophthalmic glass|
|US3296004||Aug 12, 1963||Jan 3, 1967||Pittsburgh Plate Glass Co||Neutral brown heat absorbing glass composition|
|US3296005||Dec 23, 1964||Jan 3, 1967||Pittsburgh Plate Glass Co||Bronze-smoke ophthalmic glass composition|
|US3300323||Jun 11, 1965||Jan 24, 1967||Glaverbel||Gray glass composition|
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|US4500567||Dec 19, 1983||Feb 19, 1985||Nippon Sheet Glass Co., Ltd.||Method for forming tin oxide coating|
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|FR2082647A5||Title not available|
|FR2270215A1||Title not available|
|FR2331527A1||Title not available|
|FR2682101A1||Title not available|
|GB803927A||Title not available|
|GB1163482A *||Title not available|
|GB1331492A||Title not available|
|GB1512704A||Title not available|
|GB2071082A||Title not available|
|GB2162835A||Title not available|
|GB2260978A||Title not available|
|JPS6340743A||Title not available|
|JPS57106537A||Title not available|
|WO1991007356A1||Nov 12, 1990||May 30, 1991||Libbey Owens Ford Co||Infrared and ultraviolet radiation absorbing green glass composition|
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|1||Chemical Abstracts, vol. 107, No. 18, Nov. 2, 1987, No. 160079P, p. 371.|
|2||Chemical Abstracts, vol. 88, No. 24, Jun. 12, 1978, No. 175980P, p. 356.|
|3||Chemical Abstracts, vol. 98, No. 2, Jan. 10, 1983, No. 745D, p. 177.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US8901021||Feb 14, 2011||Dec 2, 2014||Ppg Industries Ohio, Inc.||Dark privacy glass|
|US9079794||Dec 17, 2010||Jul 14, 2015||Pilkington Group Limited||Soda lime silica glass composition|
|US9120695||Aug 2, 2012||Sep 1, 2015||Kcc Corporation||Dark neutral gray glass composition with low transmittance, and glass formed therefrom|
|U.S. Classification||501/71, 501/905, 428/432, 501/904, 501/70, 428/426, 428/428|
|International Classification||C03C1/10, E06B3/02, C03C3/091, C03C4/02, C03C3/078, C03C17/23, C03C3/087|
|Cooperative Classification||Y10S501/904, Y10S501/905, C03C3/078, C03C17/23, C03C4/02, C03C3/087, C03C2217/211|
|European Classification||C03C4/02, C03C3/078, C03C3/087, C03C17/23|
|Sep 27, 1996||AS||Assignment|
Owner name: SAINT-GOBAIN VITRAGE, FRANCE
Free format text: CHANGE OF NAME;ASSIGNOR:SAINT GOBAIN VITRAGE INTERNATIONAL;REEL/FRAME:008347/0435
Effective date: 19960820
|Jun 17, 2003||CC||Certificate of correction|
|Oct 2, 2006||LAPS||Lapse for failure to pay maintenance fees|