• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a glass sheet comprising a hardened mineral glass substrate having, on one of its faces, a low-emissivity transparent coating and, on the latter, an enamel layer containing one or more ceramic pigments, the layer enamel coating covering only a part of the low-emissivity layer and leaving free another part thereof, characterized in that at least 50% by weight, preferably at least 80% by weight, and in particular at least less than 95% by weight of the ceramic pigments are chosen from ceramic pigments reflecting near-infrared radiation (NIR) having a reflectance at 1000 nm, determined according to ASTM standard E 903, at least 40% and a clarity L * less than 30. It also relates to a process for producing such a sheet and a furnace or refrigerator door containing such a sheet.
    公开号:FR3052769A1
    申请号:FR1655538
    申请日:2016-06-15
    公开日:2017-12-22
    发明作者:Benoit Rufino
    申请人:Saint Gobain Glass France SAS；
    IPC主号:
    专利说明:

    GLASS SHEET WITH EMAIL REFLECTING INFRARED RADIATION
    The present invention relates to partially enamelled glass sheets for oven doors or refrigerators and a method for producing such sheets.
    In the field of glazed oven doors or glass doors of refrigerators, whether monolithic or multi-leaf glazing, it is known to cover at least one side of at least one of the glass sheets of a low-emissivity transparent coating to improve the thermal insulation of the oven and to reduce the risk of burns when in contact with the operating oven door.
    Furthermore, it is usual, for aesthetic reasons, to partially opacify the glass sheets by a frame, generally black in color, printed by screen printing on the periphery of the glass sheets.
    There is a growing demand, particularly from furnace manufacturers, for low-emissivity transparent-layer glass sheets with an opaque enamel frame. For reasons of reduction of production costs, this layer of enamel must be formed during the step of thermal reinforcement of the glass (cooking followed by quenching).
    The creation of a black or dark enamel frame on a low-emissivity glass sheet is difficult, however. Indeed, during the heating of the printed sheet on a part of its surface with a pigmented glass paste, for example with a usual black pigment of the spinel type of chromium-copper oxide, it is frequently observed a lack of flatness of the product quenched and the non-compliance of the resulting glass sheet to the fragmentation standard for the hardened soda-lime safety glass; areas covered by enamel have a different fragmentation profile from those covered by the low-emission layer but not covered with enamel, whereas the EN 1250-1 standard requires a uniform fragmentation over the entire glass sheet.
    In some cases, it can be seen that the glass sheet breaks during quenching (rapid cooling).
    The problems described above do not exist or very little in the absence of low-emissivity transparent coating and are accentuated when the emissivity of the coating decreases. They were attributed to the difference in thermal energy absorption, received in the form of infrared radiation by the areas covered by the low emissivity coating only and those covered by the low emissivity coating and the enamel layer.
    The present invention is based on the discovery that the problems described above can be reduced or even eliminated when high-reflectance, near-infrared ceramic pigments are used for the pigmentation of enamel.
    U.S. Patent No. 5,898,180 discloses enamels for use as an inner liner for furnaces heated by visible-NIR radiation sources, such as halogenated quartz lamps. These enamels are described as having a reflectance in the wavelength range from 0.6 μιτι to 5 pm greater than 80%. The pigments reflecting the visible and infrared radiation listed in this document are TiO 2, ZnO, ZrO 2 and Sb 2 O 3. These are white pigments which, for aesthetic reasons, are unusable for the enamel of oven doors. In this field, market demand is almost exclusively for very dark enamels, preferably black enamels.
    The problem underlying the present invention is therefore to find pigments that are both highly absorbent in the visible and sufficiently reflective in the wavelength range of the IR radiation used for heating glazing before thermal quenching.
    The present invention therefore has for its first object a glass sheet comprising a tempered mineral glass substrate bearing, on one of its faces, a low-emissivity coating and, on the latter, an enamel layer containing one or more ceramic pigments. the enamel layer covering only a part of the low emissivity transparent coating and leaving free another part thereof, characterized in that at least 50% by weight of the ceramic pigments are chosen from ceramic pigments reflecting the Near infrared (NIR) radiation having a reflectance at 1000 nm, determined according to ASTM E 903, at least 40% and a clarity L * less than 30.
    The mineral glass substrate carrying the low emissivity coating and the enamel layer may in principle be any tempered or tempered mineral glass, compatible with use in an oven or refrigerator door. It is preferably a soda-lime glass with a thickness of between 2 and 6 mm, in particular between 2.5 and 4.5 mm.
    Low emissivity coatings are known as such. They generally consist of one or more layers of a transparent conductive oxide (TCO) such as tin oxide doped with fluorine or antimony, the mixed oxide of indium and tin. They may also be stacks comprising at least one thin metal layer, for example a silver layer, placed between dielectric layers. The thickness of the low-emissivity coatings is generally between 5 and 250 nm, in particular between 5 and 150 nm.
    Their emissivity, determined according to ISO 10292: 1994 (Appendix A), is advantageously between 0.01 and 0.30, preferably between 0.03 and 0.25, in particular between 0.05 and 0.20.
    The dark colored enamel layer covers only a portion of the low-emissivity coating and leaves another portion of this coating free. The surface of the low-emissivity coating covered by the enamel layer is preferably between 10% and 60%, in particular between 15 and 50%, more preferably between 20 and 40% of the total surface area of the low-emissivity coating. The enamel layer preferably covers the low-emissivity coating on the peripheral portion near the edge of the tempered mineral glass sheet, particularly in the manner of a dark colored frame or mat. to the edge of the glass sheet.
    This enamel layer is preferably opaque to visible light.
    Its optical density (D), defined by the following formula
    where / is the energy intensity transmitted over the entire spectrum of visible light and the incident energy intensity over the entire spectrum of visible light, is preferably between 1.8 and 5, in particular between 2.0 and 4, in particular between 2.2 and 3. The thickness of the enamel layer is advantageously between 5 μm and 40 μm, preferably between 7 μm and 25 μm, and in particular between 10 and 15 μm. pm.
    The enamel layer consists of a vitreous binder and ceramic pigments. In order to be able to prepare the opaque and thinnest enamels possible, it is interesting to increase as much as possible the volume fraction in ceramic pigments of the enamel. Beyond a certain limit, an increase in the pigment content results in insufficient cohesion and mechanical embrittlement of the enamel layer. For this reason, the total content of ceramic pigments in the enamel layer should generally not exceed about 40% by weight.
    In a preferred embodiment, the total content of ceramic pigments of the enamel layer is between 20% and 40% by weight, preferably between 30% and 39% by weight and in particular between 35% and 38% by weight. , based on the total weight of the enamel layer.
    All the ceramic pigments contained in the enamel layer are not necessarily pigments reflecting the infrared radiation as defined above. To see the beneficial effects of the use of such pigments, it is however necessary that they represent at least 50% by weight of all the ceramic pigments present. Preferably they represent at least 80% by weight, and in particular at least 90% by weight, ideally at least 95% by weight of all the ceramic pigments present.
    To effectively reflect infrared radiation, ceramic pigment particles must not be too small. Their diameter is advantageously of the same order of magnitude as the wavelength of the reflected infrared radiation.
    The NIR-reflecting pigments used in the present invention are therefore advantageously constituted by particles having a mean diameter of between 500 nm and 10 μm, preferably between 600 nm and 5.0 μm, in particular between 700 nm and 3 μm.
    As mentioned in the introduction, the NIR reflective ceramic pigments used in the present invention are dark in color, preferably of a color close to black. They are therefore different from the white pigments described in US Pat. No. 5,898,180, which both very effectively reflect visible light and near-infrared radiation (diffuse reflectance in the infrared greater than 80%).
    The hue of a dye or pigment is conventionally defined in the CIE color space L * a * b * defined by three magnitudes (L *, a * and b *) whose first L * denotes clarity. The value of L * ranges from 0 for black to 100 for white.
    The clarity L * of the ceramic pigments reflecting the NIR radiation used in the present invention is preferably between 1 and 20, in particular between 2 and 10.
    Examples of dark colored pigments reflecting the near-infrared (NIR) radiation that may be used in the present invention are the following products: chromium hematites doped with Al and Ti sold under the names V-780 Cool Colors IR Brown Black and V-799 IR Black Cool Colors by the company Ferro, - copper-chromium-manganese black spinels (Cl black pigment 28) sold under the trade names 7890 Meteor Black and 9875 Meteor Plus HS Jet Black by the company BASF , or Black 411 by Sphepherd, - copper-chromium-manganese-barium spinels (Cl black pigment 28) available under the names Meteor Plus Jet Black (BASF), Heucodur Brown 869 (Heubach), Heucodur Black 953 (Heubach) Heucodur Black 963, - chromium oxide hematites (Cl green pigment 17) available from Ferro under the names GEODE V-774
    Cool Colors Black, GEODE V-775 Black Cool Colors IR, GEODE Black V-776 Cool Colors Black, GEODE Black V-778 Cool Colors IR, Black GEODE 10204 IR Black Eclipse, and 0-1775B Ebony, or from the company Shepherd under the names Black 10C909 and Black 30C940; - The black spinel chromium-iron-nickel (C1 black pigment 30) sold by the company Ferro under the name GEODE 10456 Black or by the company Heubach under the name Heucodur Black 950; iron-chromium spinel spinels (Cl brown pigment 29) sold by the company Shepherd under the trade name Black 411, or by the company BASF under the trade names 9880 Meteor Plus High Jet Black, 9882 Meteor Plus Black, 9887 Meteor More High Black IR, 9889 Meteor Plus High IR Black; cobalt-chromium-iron spinels (Cl black pigment 27) available under the names Heucodur Black 955 (Heubach); copper-chromium-iron spinels (Cl black pigment 28) available under the name Heucodur Black 9-100 (Heubach); chromium oxide hematite (Cl green pigment 17) available under the name Heucodur Black 910 (Heubach); - The black iron-chromite spinels (Cl pigment brown 35) available under the names 7895 Meteor High IR Black, Heucodur Black 920 (Heubach) and Heucodur Black 940 (Heubach); - iron-chromium-manganese spinels (Cl pigment brown 29) available under the names 9880 Meteor High IR Black, 9882 Meteor Plus Black, 9887 Meteor Plus High IR Black, 9889 Meteor Plus High IR Black, - spinels manganese, bismuth, chromium-free strontium and / or vanadium, available under the names GEODE 10201 Eclipse Black (Ferro), GEODE 10202 Eclipse Black (Ferro) and GEODE 10203 Eclipse Black (Ferro).
    Of these pigments, iron chromites (Cl brown pigment and Cl pigment brown 29) and iron and nickel chromites (Cl pigment black 30) are most preferred.
    The vitreous binder which constitutes at least 60% by weight of the enamel layer, provides the link between the pigment particles and the adhesion of the enamel layer to the low-emissivity coating. The binder is generally obtained by melting a glass frit having a softening point at least 50 ° C lower than the temperature at which the glass sheet is heated prior to thermal quenching. The softening point of the vitreous binder is preferably below 590 ° C.
    The reflectance at 1000 nm (measured according to ASTM E 903) of the enamel layer of the present invention, based on the vitreous binder and the ceramic pigments as defined above, is preferably greater than 13%, in particular greater than at 15%, and more preferably above 18%. It is usually less than 70%.
    The present invention also relates to an oven door comprising at least one glass sheet according to the invention as described above.
    This oven door is in particular a multi-leaf glazing in which, when the door is installed in front of the oven cavity, the low-emissivity transparent coating is preferably turned towards the cavity of the oven.
    In such a multi-pane sealed oven, the tempered glass sheet of the present invention preferably has a soda-lime glass substrate and is preferably positioned so as not to be in direct contact with the oven cavity. . It is indeed preferable to interpose between the oven cavity and the glass sheet of the present invention a glass sheet relatively more resistant to temperature variations than a sheet of soda-lime glass.
    In one embodiment, the oven door of the present invention further comprises a sheet of borosilicate glass or soda-lime glass coated with a low emissivity layer, placed between the oven cavity and the glass sheet according to the invention. invention, thereby separating the latter from the oven cavity.
    The present invention also relates to a refrigerator door comprising at least one glass sheet according to the invention as described above.
    Finally, the subject of the present invention is a process for producing a glass sheet for an oven door or refrigerator comprising a tempered mineral glass substrate bearing, on one of its faces, a low-emissivity coating and, on this surface, ci, an enamel layer containing one or more ceramic pigments, said method comprising the following steps: - providing a mineral glass substrate bearing on at least one of these faces a transparent low-emissivity coating; applying, on only a part of the low-emissivity transparent coating, a pigmented glass paste comprising a glass frit and one or more ceramic pigments, at least 50% by weight, preferably at least 80% by weight, and in particular at least 95% by weight of the ceramic pigments being chosen from ceramic pigments reflecting near-infrared radiation (NIR) having a reflectance at 1000 nm, determined according to ASTM standard E 903, at least 40% and clarity L * less than 30; irradiating the glass sheet thus obtained by means of NIR radiation sources so as to heat it to a temperature close to its softening point; - thermal tempering of the glass sheet.
    The mineral glass substrate is preferably a float glass, pre-cut to the dimensions of the oven door or refrigerator in which the glass sheet is to be integrated. It is covered on at least one side, preferably on both sides, with a low-emissivity transparent coating, for example a transparent conductive oxide deposited by magnetron-assisted cathode sputtering or by vapor deposition (CVD, Chemical Vapor Deposition). ).
    A pigmented glass paste is prepared in a known manner by mixing a finely ground glass frit with a solution of a polymer in an organic solvent and with the one or more ceramic pigments.
    The glass paste is then applied, for example by screen printing, to a portion of the low-emissivity transparent coating in a wet thickness of a few tens of micrometers.
    After drying of the printed layer, the whole is worn in a few minutes at a temperature between 600 and 800 ° C and then quenched in a continuous or oscillating quench furnace.
    Example
    Two glass pastes having the weight composition indicated in the table below are prepared
    These two pastes are printed by screen printing in the form of a frame bordering a soda-lime glass substrate (dimensions 50 cm x 50 cm) bearing on each of its faces a coating (SGG EkoVision II) having an emissivity of 0 , 2 and which consists of the following succession of layers: Glass // Si3N4 / SiO2 / ITO / Si3N4 / SiO2 / TiOx.
    The viscosity of the pasta is about 80 poises and the thickness of the layers is about 27 μm. The printed substrates are then dried in an IR tube oven at a temperature of about 130 ° C until complete evaporation of the organic solvent.
    The two glass sheets are then worn over a period of 4 minutes at a temperature of 670 ° C by means of electrical resistors emitting infrared radiation having wavelengths up to about 5 pm, and then quenched by means of a cold air flow.
    Figure 1 shows the reflection spectrum of the UV-visible-IR radiation of the enamel containing the standard black pigment and the enamel containing the black pigment reflecting the IR radiation.
    When the comparative glass sheet is subjected to a fragmentation test according to the standard EN 1250-1, it is found that the pieces of glass are significantly smaller in the area covered by the black enamel than in the area covered only by the low emissivity coating. The difference in size between the zones is such that the glass sheet is judged to be non-compliant with the fragmentation test.
    When the enameled glass sheet according to the invention is subjected to the same fragmentation test according to the EN 1250-1 standard, the pieces of glass in the zones covered by the enamel have dimensions similar to those observed in the areas not covered by enamel. Figure 2 shows a photo of such a glass sheet according to the invention after fragmentation according to EN 1250-1.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Glass sheet comprising a tempered mineral glass substrate bearing, on one of its faces, a low-emissivity transparent coating and, on the latter, an enamel layer containing one or more ceramic pigments, the enamel layer covering only a part of the low-emissivity layer and leaving free another part thereof, characterized in that at least 50% by weight, preferably at least 80% by weight, and in particular at least 95% by weight by weight of the ceramic pigments are chosen from ceramic pigments reflecting near-infrared radiation (NIR) having a reflectance at 1000 nm, determined according to ASTM E 903, at least 40% and a clarity L * of less than 30.
    [2" id="c-fr-0002]
    2. Glass sheet according to claim 1, characterized in that the total content of ceramic pigments of the enamel layer is between 20% and 40% by weight, preferably between 30% and 39% by weight, especially between 35% and 38% by weight, based on the total weight of the enamel layer.
    [3" id="c-fr-0003]
    3. Glass sheet according to claim 1 or 2, characterized in that the clarity L * of the ceramic pigments reflecting the NIR radiation is between 1 and 20, in particular between 2 and 10.
    [4" id="c-fr-0004]
    4. Glass sheet according to one of the preceding claims, characterized in that the ceramic pigment or pigments reflecting the NIR radiation are chosen from the group consisting of C1 black pigment 27, C1 black pigment 28, C1 black pigment 30, Cl green pigment 17, Cl brown pigment 29, Cl brown pigment 35, chromium oxide hematite doped Al and Ti, manganese oxide spinel, bismuth, strontium and / or vanadium free of chromium.
    [5" id="c-fr-0005]
    5. Glass sheet according to one of the preceding claims, characterized in that the reflecting pigment or pigments NIR are selected from iron chromites and chromites of iron and nickel.
    [6" id="c-fr-0006]
    6. Glass sheet according to any one of the preceding claims, characterized in that the enamel layer has a thickness of between 5 μm and 40 μm, preferably between 7 μm and 25 μm, and in particular between 10 μm and 25 μm. 15 pm.
    [7" id="c-fr-0007]
    7. Glass sheet according to any one of the preceding claims, characterized in that the enamel layer covers the peripheral portion of the low-emissivity layer near the edge of the quenched mineral glass sheet.
    [8" id="c-fr-0008]
    8. Glass sheet according to any one of the preceding claims, characterized in that the NIR-reflecting pigments consist of particles having a mean diameter of between 500 nm and 10 μm, preferably between 600 nm and 5.0 μm. in particular between 700 nm and 3 μm.
    [9" id="c-fr-0009]
    9. Glass sheet according to any one of the preceding claims, characterized in that the enamel layer has a reflectance at 1000 nm (measured according to ASTM E 903) greater than 13%, preferably greater than 15%, greater than 18%.
    [10" id="c-fr-0010]
    10. Glass sheet according to any one of the preceding claims, characterized in that the low emissivity layer has an emissivity, determined according to ISO 10292: 1994 (Appendix A), between 0.01 and 0.30 preferably between 0.03 and 0.25, in particular between 0.05 and 0.20.
    [11" id="c-fr-0011]
    An oven door comprising at least one glass sheet according to any one of the preceding claims.
    [12" id="c-fr-0012]
    12. oven door according to claim 11, characterized in that it is a multi-sheet glazing and in that, when the door is installed on the oven, the low-emissivity layer is turned towards the cavity of the oven.
    [13" id="c-fr-0013]
    13. Oven door according to claim 11 or 12, characterized in that a sheet of borosilicate glass or soda-lime glass coated with a low-emissivity layer is placed between the glass sheet according to one of the claims. 1 to 10 and the cavity of the oven, thus separating it from the oven cavity.
    [14" id="c-fr-0014]
    Refrigerator door comprising at least one glass sheet according to any one of claims 1 to 10.
    [15" id="c-fr-0015]
    15. A method of manufacturing a glass sheet according to any one of claims 1 to 10, characterized in that it comprises - the provision of a mineral glass substrate bearing on at least one of these faces a low emissivity transparent coating; the application, on only a part of the low-emissivity transparent coating, of a pigmented glass paste comprising a glass frit and one or more ceramic pigments, at least 50% by weight, preferably at least 80% by weight , and in particular at least 95% by weight of the ceramic pigments being chosen from ceramic pigments reflecting near-infrared radiation (NIR) having a reflectance at 1000 nm, determined according to ASTM standard E 903, at least equal to 40% and a clarity L * less than 30; irradiating the glass sheet thus obtained by means of NIR radiation sources so as to heat it to a temperature close to its softening point; - thermal tempering of the glass sheet.
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    引用文献:
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    FR2810029A1|2000-06-09|2001-12-14|Saint Gobain Vitrage|Aqueous black enamel composition for a glass substrate used , e.g., as motor vehicle glazing includes sodium and/or potassium silicate, copper, iron or cobalt oxide, zinc oxide and specified glass frits|
    EP2314553A1|2009-10-16|2011-04-27|AGC Glass Europe|Enamelled reflecting glazing|
    FR3010074A1|2013-09-05|2015-03-06|Saint Gobain|METHOD FOR MANUFACTURING A MATERIAL COMPRISING A SUBSTRATE HAVING A FUNCTIONAL LAYER BASED ON TIN OXIDE AND INDIUM|
    CN2091858U|1990-06-19|1992-01-01|中国科学院广州能源研究所|Enamel solar still with inclined steps|
    US5344718A|1992-04-30|1994-09-06|Guardian Industries Corp.|High performance, durable, low-E glass|
    JP2001186967A|1999-12-28|2001-07-10|Nippon Sheet Glass Co Ltd|Glass for refrigerator-freezer and glass article using the same|
    US6485557B1|2000-07-06|2002-11-26|Dmc2 Degussa Metals Catalysts Cerdec Ag|Manganese vanadium oxide pigments|
    US6598426B2|2001-04-11|2003-07-29|Guardian Industries Corp.|Method of making a vehicle window with opaque layer|
    FR2889182B1|2005-07-29|2007-10-26|Saint Gobain|GLAZING PROVIDED WITH A STACK OF THIN LAYERS ACTING ON SOLAR RADIATION|
    CN100381516C|2006-03-30|2008-04-16|周先庭|High temperature far infrared insulated energy-saving paint and method for preparing same|
    JP5821841B2|2010-03-30|2015-11-24|旭硝子株式会社|Method and apparatus for strengthening glass plate|
    US8728502B2|2011-03-15|2014-05-20|Basf Corporation|Black effect pigment|
    FR3019173B1|2014-03-28|2016-03-25|Saint Gobain|GLAZING PROVIDED WITH A STACK OF THIN LAYERS FOR SOLAR PROTECTION|
    FR3020360B1|2014-04-24|2016-05-06|Saint-Gobain Glass France|METHOD FOR MANUFACTURING GLASS SUBSTRATE WITH PRINTED PATTERNS AND PROTECTIVE UNDERLAYER FOR SINGLE-SENSE VISION|
    EP3124876A1|2015-07-31|2017-02-01|Electrolux Appliances Aktiebolag|A heatable cavity for a kitchen appliance having a low emissivity coating|
    FR3052769B1|2016-06-15|2018-07-13|Saint-Gobain Glass France|GLASS SHEET WITH EMAIL REFLECTING INFRARED RADIATION|FR3052769B1|2016-06-15|2018-07-13|Saint-Gobain Glass France|GLASS SHEET WITH EMAIL REFLECTING INFRARED RADIATION|
    DE102017127624A1|2017-11-22|2019-05-23|Schott Ag|Coated glass or glass-ceramic substrate, coating comprising closed pores and method for coating a substrate|
    KR20200124506A|2019-04-24|2020-11-03|쌩-고벵 글래스 프랑스|Glass frit, coated article including a black enamel coating formed from the same, and method for manufacturing the coated article|
    WO2022018078A1|2020-07-22|2022-01-27|Saint-Gobain Glass France|Photovoltaic panel|
    法律状态:
    2017-06-23| PLFP| Fee payment|Year of fee payment: 2 |
    2017-12-22| PLSC| Search report ready|Effective date: 20171222 |
    2018-06-25| PLFP| Fee payment|Year of fee payment: 3 |
    2020-06-29| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1655538A|FR3052769B1|2016-06-15|2016-06-15|GLASS SHEET WITH EMAIL REFLECTING INFRARED RADIATION|
    FR1655538|2016-06-15|FR1655538A| FR3052769B1|2016-06-15|2016-06-15|GLASS SHEET WITH EMAIL REFLECTING INFRARED RADIATION|
    MX2018015579A| MX2018015579A|2016-06-15|2017-06-14|Glass sheet with enamel reflecting infrared radiation.|
    US16/308,596| US10954158B2|2016-06-15|2017-06-14|Glass sheet with enamel reflecting infrared radiation|
    CA3025657A| CA3025657A1|2016-06-15|2017-06-14|Glass sheet with enamel reflecting infrared radiation|
    RU2019100529A| RU2733926C2|2016-06-15|2017-06-14|Glass sheet with enamel reflecting infrared radiation|
    PL17740049T| PL3472114T3|2016-06-15|2017-06-14|Glass sheet with enamel reflecting infrared radiation|
    BR112018074844-7A| BR112018074844A2|2016-06-15|2017-06-14|Enameled glass sheet that reflects infrared radiation|
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    PCT/FR2017/051534| WO2017216483A1|2016-06-15|2017-06-14|Glass sheet with enamel reflecting infrared radiation|
    ES17740049T| ES2790893T3|2016-06-15|2017-06-14|Glass sheet with infrared radiation reflective enamel|
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