EP2911988A1 - Method for the production of thin sheet glass - Google Patents

Method for the production of thin sheet glass

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Publication number
EP2911988A1
EP2911988A1 EP13795836.9A EP13795836A EP2911988A1 EP 2911988 A1 EP2911988 A1 EP 2911988A1 EP 13795836 A EP13795836 A EP 13795836A EP 2911988 A1 EP2911988 A1 EP 2911988A1
Authority
EP
European Patent Office
Prior art keywords
glass
textile
bath
molten
forming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13795836.9A
Other languages
German (de)
French (fr)
Inventor
René Gy
Mathieu Joanicot
Anne CHOULET
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Saint Gobain Adfors SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Saint Gobain Adfors SAS
Compagnie de Saint Gobain SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saint Gobain Glass France SAS, Saint Gobain Adfors SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP2911988A1 publication Critical patent/EP2911988A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/1095—Coating to obtain coated fabrics
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/42—Coatings containing inorganic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses

Definitions

  • the present invention relates to a new method of manufacturing flat glass, in particular thin glass sheets comprising a glass textile incorporated in a glass matrix.
  • the present invention provides a replacement product for known thin and ultrathin glasses and a considerably simpler manufacturing process than the draw melting process.
  • the thin glasses of the present invention have an optical quality (transparency) lower than that of known thin glasses. However, they have a surface quality satisfactory, or even equivalent to that of film glasses. They are made from cheap raw materials available in large quantities and in different qualities.
  • the idea underlying the present invention was to take advantage of the similarity between glass textiles and film glasses. These two types of products have in fact a similar chemical composition, geometry and mechanical behavior and are distinguished mainly by their fluid permeability and transparency.
  • the method of the present invention reduces or even eliminates the permeability of glass textiles to fluids and increases their transparency to light, thereby bringing them closer to thin and ultrathin glasses.
  • the apertures are filled, the diffusing interfaces are reduced and the surface of a glass textile is smoothed by incorporating it into a glass matrix by immersion in a molten glass bath. During this impregnation by immersion, the glass fabric is not completely melted, which guarantees the good mechanical strength of the assembly during the cooling step, thus allowing the application of a uniform tensile force and the obtaining a good flatness.
  • the process of the present invention is distinguished by a great deal of flexibility. Indeed, both the glass fabric and the glass matrix can be independently selected from a very large number of products available on the market with, as the only constraint, the need for a matrix material having a lower softening temperature. to that of the glass textile.
  • the method of the present invention can be implemented with equipment that requires relatively little heavy investment, which is a considerable advantage over the float and merge draw processes.
  • the subject of the present invention is therefore a flat glass manufacturing process comprising, successively
  • the term "softening temperature” refers to the so-called Littleton temperature, also referred to as Littleton's point, determined in accordance with ASTM C338. This is the temperature at which the viscosity of a fiberglass measured by this method is 10 6 6 Pa.s.
  • the term "melted glass composition” or "molten glass bath” means a fluid glass composition heated to a temperature above its Littleton softening point. Before or at the time of immersion of the glass textile in the molten glass composition, the latter is preferably heated to a temperature at least 100 ° C higher, preferably at least 200 ° C higher, at its temperature. softening point Littleton.
  • the glass is heated to a temperature significantly above its softening temperature so as to be available in the form of a glass bath having a sufficiently low viscosity, preferably a viscosity between 10 and 10 6 Pa.s, preferably between 10 2 and 10 5 Pa.s and in particular between 10 3 and 10 4 Pa.s.
  • Step (a) comprises immersing the glass textile in said bath of molten glass, or alternatively applying a film of the molten glass composition to the glass fabric by other means. Preferably all the glass fabric is thus coated with liquid glass.
  • the product obtained has an asymmetric structure where, on one side, the textile texture of the support is totally planarized by covering with the glass film while on the other side, the texture is still perfectly apparent and exposed.
  • the passage of the glass textile in a glass bath leads to a symmetrical structure where the two sides of the product are planarized by a glass layer.
  • the glass cloth impregnated with molten glass is then removed from the glass bath so as to remove excess glass and limit the overall thickness of the final glass sheet.
  • the excess glass can flow freely from the impregnated glass textile or the impregnated glass fabric can be passed through a slot or scraping system.
  • the molten glass is sufficiently fluid to flow spontaneously from the impregnated glass textile.
  • the products obtained by the process of the present invention are "flat" products in the sense that they generally retain the geometry of the textile, characterized by two major surfaces parallel to each other, the method of the present invention is not limited to perfectly flat products.
  • the first tests performed by the Applicant have resulted in materials that are very satisfactory from an aesthetic point of view and it is quite possible to use them for the manufacture of decorative objects of very different shapes, such as sections, tubes, folded or corrugated walls, etc.
  • the products obtained by the process of the present invention preferably have both a flat and a flat shape.
  • it is essential to stretch the glass fabric at least during the cooling step and preferably throughout the process.
  • the glass textile is therefore subjected to a tensile force in at least one direction in the plane of the glass textile, throughout the duration of step (a) and (b) and this force traction is preferably maintained, during step (c), at least until the stiffening of the product obtained.
  • This energizing of the glass textile during the step of immersing and removing the glass textile and the cooling step is perfectly compatible with and even necessary for the implementation of a continuous process which represents a method of preferred embodiment of the present invention.
  • the glass textile is a continuous strip and the steps (a), (b) and (c) are continuous steps implemented from upstream to downstream in the process line, the direction of traction being parallel to the scroll direction of the glass textile continuous strip.
  • the glass textile may be a nonwoven or a woven.
  • the number of warp fibers and / or the number of weft fibers is typically between 3 and 100 per cm, preferably between 10 and 80 per cm.
  • the object of the present invention is to fill all the holes of the glass textile. To achieve this goal, it is essential to ensure that the openings of the starting textile are not too large.
  • woven or non-woven glass fabrics with openings having an average equivalent diameter of less than 1 mm, preferably less than 0.1 mm, will preferably be chosen.
  • the grammage of the glass textiles used is generally between 50 and 500 g / m 2 , preferably between 80 and 400 g / m 2 , and in particular between 100 and 200 g / m 2 .
  • the amount of glass applied as a molten glass composition is in the range of from 100 to 2000 g / m 2 , preferably from 200 to 1500 g / m 2 .
  • the glass cloth impregnated with molten glass is cooled (step (c)).
  • This cooling can be passively or in a controlled manner, for example by maintaining the impregnated textile in a hot environment. In order to ensure a good homogeneity of temperature throughout the cooling step, it may also be useful to heat some areas likely to cool more quickly than others.
  • the hot glass textile leaving step (b) preferably does not come into contact with any solid or liquid until it has cooled to a temperature at least 50.degree. C., preferably at least 100.degree. C at the softening temperature of the glass forming the molten glass composition.
  • the refractive index of the glass forming the glass bath should be substantially identical to that of glass forming the glass textile.
  • Another phenomenon explaining the high diffusivity of the products prepared in the manner described in the examples below is the presence of numerous gas bubbles.
  • the number of diffusing bubbles can certainly be reduced by impregnating the glass with a composition of melted glass and refined.
  • Such a flat product, or glass sheet, capable of being manufactured by a method as described above is also an object of the present invention.
  • This sheet of glass preferably has a thickness of between 50 ⁇ and 1000 ⁇ , in particular between 100 ⁇ and 800 ⁇ .
  • the structure of the glass textile can be visible by transparency to the naked eye. It can also be masked by a highly diffusing glass film, or it may no longer be visible because of the disappearance of the interfaces between the textile material and the enamel surrounding it.
  • Figure 1 shows a glass fabric having a basis weight of 165 g / m 2 .
  • This textile was immersed in a bath of molten glass, removed and cooled. It can be seen in FIG. 2 that the formed glass matrix is almost perfectly transparent and the textile structure clearly visible.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Woven Fabrics (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention relates to a method for the production of flat glass, comprising successively: (a) immersion of a glass textile in a molten-glass bath such as to obtain a glass textile impregnated with molten glass, the glass forming the fibres of the glass textile having a softening temperature above that of the molten glass bath; (b) removal of the impregnated textile from the molten glass bath; and (c) cooling of the impregnated glass textile removed from the molten glass bath such as to obtain a glass sheet. The invention also relates to a glass sheet produced using such a method.

Description

PROCEDE DE FABRICATION DE VERRE MINCE  METHOD FOR MANUFACTURING THIN GLASS
La présente invention concerne un nouveau procédé de fabrication de verre plat, en particulier de minces feuilles de verre comprenant un textile de verre incorporé dans une matrice de verre. The present invention relates to a new method of manufacturing flat glass, in particular thin glass sheets comprising a glass textile incorporated in a glass matrix.
De nombreux fabricants de verre proposent depuis quelques années des verres dits « pelliculaires » ou « ultraminces » ayant une épaisseur comprise entre quelques dizaines de micromètres et environ 200 μΐη. Ces verres, fabriqués par procédé float ou fusion draw, sont disponibles en grand format ou sous forme de bande continue. Les plus minces sont flexibles et peuvent être enroulés. Cette flexibilité permet de les utiliser dans des procédés industriels réservés classiquement aux films et feuilles en matières plastiques, notamment dans des étapes de type déroulement-enroulement {roll-to-roll).  Many glass manufacturers have been offering for some years so-called "pellicular" or "ultrathin" glasses having a thickness of between a few tens of micrometers and about 200 μΐη. These glasses, made by float or fusion draw, are available in large format or as a continuous strip. The thinnest are flexible and can be rolled up. This flexibility makes it possible to use them in industrial processes conventionally reserved for films and sheets of plastics, in particular in roll-to-roll stages.
Le procédé fusion draw donne des verres minces, transparents, qui se distinguent par un lissé de surface exceptionnel particulièrement important dans des applications de haute technologie telles que les écrans LCD. C'est toutefois un procédé complexe, peu productif et difficile à maîtriser et le coût élevé des produits est rédhibitoire pour de nombreuses applications.  The merger draw process produces thin, transparent glasses that stand out for their exceptional surface smoothness, which is particularly important in high-tech applications such as LCD screens. However, it is a complex process, unproductive and difficult to control and the high cost of the products is prohibitive for many applications.
La présente invention propose un produit de remplacement des verres minces et ultraminces connus et un procédé de fabrication considérablement plus simple que le procédé fusion draw.  The present invention provides a replacement product for known thin and ultrathin glasses and a considerably simpler manufacturing process than the draw melting process.
La plupart des verres minces de la présente invention ont une qualité optique (transparence) inférieure à celle des verres minces connus. Ils présentent toutefois une qualité de surface satisfaisante, voire équivalente à celle des verres pelliculaires. Ils sont fabriqués à partir de matières premières bon marché disponibles en grande quantité et en différentes qualités.  Most of the thin glasses of the present invention have an optical quality (transparency) lower than that of known thin glasses. However, they have a surface quality satisfactory, or even equivalent to that of film glasses. They are made from cheap raw materials available in large quantities and in different qualities.
L'idée à la base de la présente invention a été de mettre à profit la similitude entre les textiles de verre et les verres pelliculaires. Ces deux types de produits présentent en effet une composition chimique, une géométrie et un comportement mécanique semblables et se distinguent principalement par leur perméabilité aux fluides et leur transparence.  The idea underlying the present invention was to take advantage of the similarity between glass textiles and film glasses. These two types of products have in fact a similar chemical composition, geometry and mechanical behavior and are distinguished mainly by their fluid permeability and transparency.
Le procédé de la présente invention réduit, voire supprime la perméabilité des textiles de verre aux fluides et augmente leur transparence à la lumière, les rapprochant ainsi des verres minces et ultraminces. Pour atteindre cet objectif, on comble les ouvertures, on réduit les interfaces diffusantes et on lisse la surface d'un textile de verre en l'incorporant dans une matrice de verre par immersion dans un bain verre fondu. Lors de cette imprégnation par immersion le textile de verre n'est pas totalement fondu ce qui garantit la bonne tenue mécanique de l'ensemble au cours de l'étape de refroidissement, permettant ainsi l'application d'une force de traction uniforme et l'obtention d'une bonne planéité. The method of the present invention reduces or even eliminates the permeability of glass textiles to fluids and increases their transparency to light, thereby bringing them closer to thin and ultrathin glasses. To achieve this objective, the apertures are filled, the diffusing interfaces are reduced and the surface of a glass textile is smoothed by incorporating it into a glass matrix by immersion in a molten glass bath. During this impregnation by immersion, the glass fabric is not completely melted, which guarantees the good mechanical strength of the assembly during the cooling step, thus allowing the application of a uniform tensile force and the obtaining a good flatness.
Le procédé de la présente invention se distingue par une très grande souplesse. En effet, à la fois le textile de verre et la matrice de verre peuvent être choisis indépendamment parmi un très grand nombre de produits disponibles sur le marché avec, comme seule contrainte, la nécessité d'un matériau de matrice ayant une température de ramollissement inférieure à celle du textile de verre. Le procédé de la présente invention peut être mis en œuvre avec des équipements qui demandent assez peu d'investissements lourds, ce qui représente un avantage considérable par rapport aux procédés float et fusion draw.  The process of the present invention is distinguished by a great deal of flexibility. Indeed, both the glass fabric and the glass matrix can be independently selected from a very large number of products available on the market with, as the only constraint, the need for a matrix material having a lower softening temperature. to that of the glass textile. The method of the present invention can be implemented with equipment that requires relatively little heavy investment, which is a considerable advantage over the float and merge draw processes.
La présente invention a ainsi pour objet un procédé de fabrication de verre plat comprenant, successivement  The subject of the present invention is therefore a flat glass manufacturing process comprising, successively
(a) l'immersion d'un textile de verre dans un bain de verre fondu de manière à obtenir un textile de verre imprégné de verre fondu, le verre formant les fibres du textile de verre ayant une température de ramollissement supérieure à celle du bain de verre fondu,  (a) immersing a glass textile in a bath of molten glass so as to obtain a glass textile impregnated with molten glass, the glass forming the fibers of the glass fabric having a softening temperature greater than that of the bath molten glass,
(b) le retrait du textile imprégné du bain de verre fondu, et  (b) removing the textile impregnated from the molten glass bath, and
(c) le refroidissement du textile de verre imprégné et retiré du bain de verre fondu de manière à obtenir une feuille de verre.  (c) cooling the glass fabric impregnated and removed from the molten glass bath to obtain a glass sheet.
Dans la présente demande le terme « température de ramollissement » désigne la température dite de Littleton, également appelée point de Littleton, déterminée conformément à la norme ASTM C338. Il s'agit de la température à laquelle la viscosité d'une fibre de verre mesurée selon cette méthode est égale à 106'6 Pa.s. As used herein, the term "softening temperature" refers to the so-called Littleton temperature, also referred to as Littleton's point, determined in accordance with ASTM C338. This is the temperature at which the viscosity of a fiberglass measured by this method is 10 6 6 Pa.s.
On entend dans la présente demande par « composition de verre fondu » ou « bain de verre fondu », une composition fluide de verre chauffée jusqu'à une température supérieure à son point de ramollissement Littleton. Avant ou au moment de l'immersion du textile de verre dans la composition de verre fondu, cette dernière est de préférence chauffée à une température supérieure d'au moins 100 °C, de préférence supérieure d'au moins 200 °C, à son point de ramollissement Littleton. As used herein, the term "melted glass composition" or "molten glass bath" means a fluid glass composition heated to a temperature above its Littleton softening point. Before or at the time of immersion of the glass textile in the molten glass composition, the latter is preferably heated to a temperature at least 100 ° C higher, preferably at least 200 ° C higher, at its temperature. softening point Littleton.
Avant l'étape (a) du procédé de l'invention le verre est chauffé à une température significativement supérieure à sa température de ramollissement de manière à être disponible sous forme d'un bain de verre ayant une viscosité suffisamment faible, de préférence une viscosité comprise entre 10 et 106 Pa.s, de préférence entre 102 et 105 Pa.s et en particulier entre 103 et 104 Pa.s. Before step (a) of the process of the invention the glass is heated to a temperature significantly above its softening temperature so as to be available in the form of a glass bath having a sufficiently low viscosity, preferably a viscosity between 10 and 10 6 Pa.s, preferably between 10 2 and 10 5 Pa.s and in particular between 10 3 and 10 4 Pa.s.
L'étape (a) comprend l'immersion du textile de verre dans ledit bain de verre fondu, ou bien l'application d'un film de la composition de verre fondu sur le textile de verre par un autre moyen. De préférence l'ensemble du textile de verre est ainsi enduit de verre liquide. Lorsque la composition de verre fondu est suffisamment visqueuse et appliquée sur une seule face du textile de verre, le produit obtenu présente une structure asymétrique où, sur une face, la texture textile du support est totalement planarisée par recouvrement avec le film de verre tandis que, sur l'autre face, la texture est encore parfaitement apparente et exposée. Le passage du textile de verre dans un bain de verre aboutit bien entendu à une structure symétrique où les deux faces du produit sont planarisées par une couche de verre.  Step (a) comprises immersing the glass textile in said bath of molten glass, or alternatively applying a film of the molten glass composition to the glass fabric by other means. Preferably all the glass fabric is thus coated with liquid glass. When the molten glass composition is sufficiently viscous and applied to a single face of the glass textile, the product obtained has an asymmetric structure where, on one side, the textile texture of the support is totally planarized by covering with the glass film while on the other side, the texture is still perfectly apparent and exposed. The passage of the glass textile in a glass bath of course leads to a symmetrical structure where the two sides of the product are planarized by a glass layer.
Le textile de verre imprégné de verre fondu est ensuite retiré du bain de verre de manière à éliminer l'excédent de verre et de limiter l'épaisseur globale de la feuille de verre finale. L'excédent de verre peut s'écouler librement du textile de verre imprégné ou bien on peut faire passer le textile de verre imprégné à travers une fente ou un système de raclage. De préférence le verre fondu est suffisamment fluide pour s'écouler spontanément du textile de verre imprégné.  The glass cloth impregnated with molten glass is then removed from the glass bath so as to remove excess glass and limit the overall thickness of the final glass sheet. The excess glass can flow freely from the impregnated glass textile or the impregnated glass fabric can be passed through a slot or scraping system. Preferably the molten glass is sufficiently fluid to flow spontaneously from the impregnated glass textile.
Bien que les produits obtenus par le procédé de la présente invention soient des produits « plats » au sens où ils conservent globalement la géométrie du textile, caractérisée par deux surfaces principales parallèles l'une à l'autre, le procédé de la présente invention n'est nullement limité à des produits parfaitement plans. Les premiers essais effectués par la Demanderesse ont abouti en effet à des matériaux qui sont très satisfaisants d'un point de vue esthétique et il est tout à fait envisageable de les utiliser pour la fabrication d'objets décoratifs de formes très diverses, tels que des coupes, tubes, parois pliées ou ondulées etc. Although the products obtained by the process of the present invention are "flat" products in the sense that they generally retain the geometry of the textile, characterized by two major surfaces parallel to each other, the method of the present invention is not limited to perfectly flat products. The first tests performed by the Applicant have resulted in materials that are very satisfactory from an aesthetic point of view and it is quite possible to use them for the manufacture of decorative objects of very different shapes, such as sections, tubes, folded or corrugated walls, etc.
Dans la perspective d'applications plus techniques, les produits obtenus par le procédé de la présente invention ont toutefois de préférence une forme à la fois plate et plane. Pour arriver à une planéité satisfaisante du produit final, il est indispensable de tendre le textile de verre au moins pendant l'étape de refroidissement et de préférence pendant toute la durée du procédé.  In view of more technical applications, however, the products obtained by the process of the present invention preferably have both a flat and a flat shape. To achieve a satisfactory flatness of the final product, it is essential to stretch the glass fabric at least during the cooling step and preferably throughout the process.
Dans un mode de réalisation préféré le textile de verre est par conséquent soumis à une force de traction selon au moins une direction dans le plan du textile de verre, pendant toute la durée de l'étape (a) et (b) et cette force de traction est de préférence maintenue, au cours de l'étape (c), au moins jusqu'à la rigidification du produit obtenu.  In a preferred embodiment, the glass textile is therefore subjected to a tensile force in at least one direction in the plane of the glass textile, throughout the duration of step (a) and (b) and this force traction is preferably maintained, during step (c), at least until the stiffening of the product obtained.
Cette mise sous tension du textile de verre pendant l'étape d'immersion et de retrait du textile de verre et l'étape de refroidissement est parfaitement compatible avec et même nécessaire à la mise en œuvre d'un procédé continu qui représente un mode de réalisation préféré de la présente invention.  This energizing of the glass textile during the step of immersing and removing the glass textile and the cooling step is perfectly compatible with and even necessary for the implementation of a continuous process which represents a method of preferred embodiment of the present invention.
Dans un tel procédé continu, le textile de verre est une bande continue et les étapes (a), (b) et (c) sont des étapes continues mises en œuvre d'amont en aval dans la ligne de procédé, la direction de traction étant parallèle à la direction de défilement de la bande continue de textile de verre.  In such a continuous process, the glass textile is a continuous strip and the steps (a), (b) and (c) are continuous steps implemented from upstream to downstream in the process line, the direction of traction being parallel to the scroll direction of the glass textile continuous strip.
Le textile de verre peut être un non-tissé ou bien un tissé. Lorsqu'il s'agit d'un tissé, le nombre de fibres de chaîne et/ou le nombre de fibres de trame est typiquement compris entre 3 et 100 par cm, de préférence entre 10 et 80 par cm.  The glass textile may be a nonwoven or a woven. When it is a woven, the number of warp fibers and / or the number of weft fibers is typically between 3 and 100 per cm, preferably between 10 and 80 per cm.
L'objectif de la présente invention est de combler l'ensemble des trous du textile de verre. Pour atteindre ce but, il est indispensable de veiller à ce que les ouvertures du textile de départ ne soient pas trop grandes. On choisira donc de préférence des textiles de verre, tissés ou non-tissés, avec des ouvertures présentant un diamètre équivalent moyen inférieur à 1 mm, de préférence inférieur à 0,1 mm.  The object of the present invention is to fill all the holes of the glass textile. To achieve this goal, it is essential to ensure that the openings of the starting textile are not too large. Thus, woven or non-woven glass fabrics with openings having an average equivalent diameter of less than 1 mm, preferably less than 0.1 mm, will preferably be chosen.
Le grammage des textiles de verre utilisés est généralement compris entre 50 et 500 g/m2, de préférence entre 80 et 400 g/m2, et en particulier entre 100 et 200 g/m2. La quantité de verre appliquée sous forme de composition de verre fondu est comprise dans l'intervalle allant de 100 à 2000 g/m2, de préférence de 200 à 1500 g/m2. The grammage of the glass textiles used is generally between 50 and 500 g / m 2 , preferably between 80 and 400 g / m 2 , and in particular between 100 and 200 g / m 2 . The amount of glass applied as a molten glass composition is in the range of from 100 to 2000 g / m 2 , preferably from 200 to 1500 g / m 2 .
Après application de la quantité de verre fondu souhaitée, le textile de verre imprégné de verre fondu est refroidi (étape (c)). Ce refroidissement peut se faire passivement ou de manière contrôlée, par exemple par maintien du textile imprégné dans un environnement chaud. Afin de veiller à une bonne homogénéité de température tout au long de l'étape de refroidissement, il peut également être utile de chauffer certaines zones susceptibles de se refroidir plus rapidement que d'autres.  After applying the desired amount of molten glass, the glass cloth impregnated with molten glass is cooled (step (c)). This cooling can be passively or in a controlled manner, for example by maintaining the impregnated textile in a hot environment. In order to ensure a good homogeneity of temperature throughout the cooling step, it may also be useful to heat some areas likely to cool more quickly than others.
Le textile de verre chaud sortant de l'étape (b) ne vient de préférence en contact avec aucun solide ni liquide avant de s'être refroidi à une température inférieure d'au moins 50 °C, de préférence d'au moins 100 °C à la température de ramollissement du verre formant la composition de verre fondu.  The hot glass textile leaving step (b) preferably does not come into contact with any solid or liquid until it has cooled to a temperature at least 50.degree. C., preferably at least 100.degree. C at the softening temperature of the glass forming the molten glass composition.
Certains échantillons préparés par la Demanderesse se sont avérés être très diffusants. Cette forte diffusion a été attribuée, d'une part, à la différence importante entre l'indice de réfraction du verre formant le textile et celui du verre formant la matrice. Lorsqu'on cherche à obtenir une forte diffusivité, par exemple dans le domaine des substrats pour OLED, on veillera à ce que l'indice de réfraction du verre formant la matrice soit supérieur d'au moins 0,01 , de préférence d'au moins 0,05 à l'indice de réfraction du textile de verre.  Certain samples prepared by the Applicant have proved to be very diffusive. This strong diffusion was attributed, on the one hand, to the important difference between the refractive index of the glass forming the textile and that of the glass forming the matrix. When one seeks to obtain a high diffusivity, for example in the field of substrates for OLED, it will be ensured that the refractive index of the glass forming the matrix is greater by at least 0.01, preferably from minus 0.05 to the refractive index of the glass textile.
Par contre, lorsqu'on cherchera à augmenter le plus possible la transparence des produits finals, l'indice de réfraction du verre formant le bain de verre devra être sensiblement identique à celui du verre formant le textile de verre.  On the other hand, when it is sought to increase as much as possible the transparency of the final products, the refractive index of the glass forming the glass bath should be substantially identical to that of glass forming the glass textile.
Un autre phénomène expliquant la forte diffusivité des produits préparés de la manière décrite dans les exemples ci-après est la présence de nombreuses bulles de gaz. Le nombre de bulles diffusantes pourra certainement être réduit en imprégnant le verre avec une composition de verre fondu et affiné.  Another phenomenon explaining the high diffusivity of the products prepared in the manner described in the examples below is the presence of numerous gas bubbles. The number of diffusing bubbles can certainly be reduced by impregnating the glass with a composition of melted glass and refined.
La microscopie sur des coupes transversales des produits a montré que la forte diffusivité est également due, au moins en partie, à un mouillage insuffisant des fibres de verre par le verre liquide, empêchant une pénétration satisfaisante de la matrice au cœur des fibres multi-filaments. La Demanderesse pense qu'il est possible d'atténuer, voire de surmonter, ce problème en limitant la viscosité du verre liquide à des valeurs inférieures à 104 Pa.s, voire inférieures à 103 Pa.s et/ou en prolongeant le temps de séjour du textile de verre dans le bain de verre fondu. Microscopy on cross sections of the products showed that the high diffusivity is also due, at least in part, to insufficient wetting of the glass fibers by the liquid glass, preventing satisfactory penetration of the matrix at the core of the multi-filament fibers . The Applicant believes that it is possible to mitigate or even overcome this problem by limiting the viscosity of the liquid glass to values of less than 10 4 Pa.s, or even less than 10 3 Pa.s and / or by prolonging the time of stay of the textile of glass in the bath of molten glass.
A la connaissance de la Demanderesse, il n'existe pas à ce jour de description d'un produit plat obtenu par combinaison d'un textile de verre et d'une composition de verre fondu. La demande internationale WO 88/05031 divulgue certes des plaques de verre renforcées par des structures textiles, en particulier par des textiles de verre, mais ces plaques ont des épaisseurs considérablement plus importantes à celles du verre mince de la présente invention.  To the knowledge of the Applicant, there is as yet no description of a flat product obtained by combining a glass textile and a molten glass composition. International application WO 88/05031 discloses glass plates reinforced by textile structures, in particular glass textiles, but these plates have thicknesses considerably greater than those of the thin glass of the present invention.
Un tel produit plat, ou feuille de verre, susceptible d'être fabriqué par un procédé tel que décrit ci-dessus constitue par conséquent également un objet de la présente invention.  Such a flat product, or glass sheet, capable of being manufactured by a method as described above is also an object of the present invention.
Cette feuille de verre présente de préférence une épaisseur comprise entre 50 μΐη et 1000 μΐτι, en particulier entre 100 μΐη et 800 μΐη.  This sheet of glass preferably has a thickness of between 50 μΐη and 1000 μΐτι, in particular between 100 μΐη and 800 μΐη.
Dans cette feuille de verre, la structure du textile de verre peut être visible par transparence à l'œil nu. Elle peut également être masquée par un film de verre hautement diffusant, ou bien elle peut ne plus être visible du fait de la disparition des interfaces entre le matériau textile et l'émail enveloppant celui-ci.  In this sheet of glass, the structure of the glass textile can be visible by transparency to the naked eye. It can also be masked by a highly diffusing glass film, or it may no longer be visible because of the disappearance of the interfaces between the textile material and the enamel surrounding it.
Exemple Example
La figure 1 montre un textile de verre présentant un grammage de 165 g/m2. Ce textile a été immergé dans un bain de verre fondu, retiré et refroidi. On voit sur la figure 2 que la matrice de verre formée est presque parfaitement transparente et la structure textile bien visible. Figure 1 shows a glass fabric having a basis weight of 165 g / m 2 . This textile was immersed in a bath of molten glass, removed and cooled. It can be seen in FIG. 2 that the formed glass matrix is almost perfectly transparent and the textile structure clearly visible.

Claims

REVENDICATIONS
1 . Procédé de fabrication de verre plat comprenant, successivement1. Method for manufacturing flat glass comprising, successively
(a) l'immersion d'un textile de verre dans un bain de verre fondu de manière à obtenir un textile de verre imprégné de verre fondu, le verre formant les fibres du textile de verre ayant une température de ramollissement supérieure à celle du bain de verre fondu, (a) immersing a glass textile in a bath of molten glass so as to obtain a glass textile impregnated with molten glass, the glass forming the fibers of the glass fabric having a softening temperature greater than that of the bath molten glass,
(b) le retrait du textile imprégné du bain de verre fondu, et  (b) removing the textile impregnated from the molten glass bath, and
(c) le refroidissement du textile de verre imprégné et retiré du bain de verre fondu de manière à obtenir une feuille de verre.  (c) cooling the glass fabric impregnated and removed from the molten glass bath to obtain a glass sheet.
2. Procédé selon la revendication précédente, caractérisé par le fait que la température de ramollissement du verre formant les fibres du textile de verre est supérieure d'au moins 100 °C, de préférence d'au moins 200 °C, à celle du verre formant le bain de verre fondu.  2. Method according to the preceding claim, characterized in that the softening temperature of the glass-forming glass fiber glass is at least 100 ° C, preferably at least 200 ° C, greater than that of glass. forming the molten glass bath.
3. Procédé selon l'une quelconque des revendications précédentes, caractérisé par le fait que le textile de verre est soumis à une force de traction selon au moins une direction dans le plan du textile de verre, pendant toute la durée de l'étape (a) et (b) et par le fait que cette force de traction est maintenue au cours de l'étape (c) au moins jusqu'à la rigidification du produit obtenu.  3. Method according to any one of the preceding claims, characterized in that the glass textile is subjected to a tensile force in at least one direction in the plane of the glass textile, throughout the duration of the step ( a) and (b) and in that this traction force is maintained during step (c) at least until the stiffening of the product obtained.
4. Procédé selon l'une des revendications précédentes, caractérisé par le fait que le textile de verre présente un grammage compris entre 50 et 500 g/m2, de préférence entre 80 et 400 g/m2, en particulier entre 100 et 200 g/m2. 4. Method according to one of the preceding claims, characterized in that the glass textile has a basis weight between 50 and 500 g / m 2 , preferably between 80 and 400 g / m 2 , in particular between 100 and 200 g / m 2 .
5. Procédé selon l'une quelconque des revendications précédentes, caractérisé par le fait la quantité de verre appliquée sous forme de composition de verre fondu est comprise dans l'intervalle allant de 100 à 2000 g/m2, de préférence de 200 à 1500 g/m2. 5. Method according to any one of the preceding claims, characterized in that the amount of glass applied in the form of molten glass composition is in the range of 100 to 2000 g / m 2 , preferably 200 to 1500 g / m 2 .
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé par le fait que le diamètre équivalent moyen des ouvertures du textile de verre est inférieur à 1 mm, de préférence inférieur à 0,1 mm.  6. Method according to any one of the preceding claims, characterized in that the average equivalent diameter of the openings of the glass textile is less than 1 mm, preferably less than 0.1 mm.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé par le fait que le textile de verre est un tissé présentant un nombre de fibres de chaîne et/ou un nombre de fibres de trame compris entre 3 et 100 /cm, de préférence entre 10 et 80 /cm. 7. Method according to any one of the preceding claims, characterized in that the glass textile is a woven having a number of warp fibers and / or a number of weft fibers between 3 and 100 / cm, preferably between 10 and 80 / cm.
8. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé par le fait que le textile de verre est un non-tissé. 8. Method according to any one of claims 1 to 6, characterized in that the glass textile is a nonwoven.
9. Procédé selon l'une quelconque des revendications précédentes, caractérisé par le fait que le textile de verre chaud sortant de l'étape (b), ne vient en contact avec aucun solide ni liquide avant refroidissement à une température inférieure d'au moins 50 °C, de préférence d'au moins 100 °C à la température de ramollissement du verre formant la composition de verre fondu.  9. Process according to any one of the preceding claims, characterized in that the hot glass textile leaving step (b) does not come into contact with any solid or liquid before cooling to a temperature below at least 50 ° C, preferably at least 100 ° C at the softening temperature of the glass forming the molten glass composition.
10. Procédé selon l'une quelconque des revendications précédentes, caractérisé par le fait que l'indice de réfraction du verre formant le bain de verre est sensiblement identique à celui du verre formant le textile de verre.  10. Method according to any one of the preceding claims, characterized in that the refractive index of the glass forming the glass bath is substantially identical to that of glass forming the glass textile.
1 1 . Procédé selon l'une quelconque des revendications 1 à 9, caractérisé par le fait que l'indice de réfraction du verre formant le bain de verre est supérieur d'au moins 0,01 , de préférence d'au moins 0,05 à l'indice de réfraction du textile de verre.  1 1. Process according to any one of Claims 1 to 9, characterized in that the refractive index of the glass forming the glass bath is at least 0.01, preferably at least 0.05 to 1, refractive index of the glass textile.
12. Feuille de verre susceptible d'être fabriquée par un procédé selon l'une quelconque des revendications précédentes.  12. Glass sheet capable of being manufactured by a method according to any one of the preceding claims.
13. Feuille de verre selon la revendication 12, caractérisée par le fait qu'elle présente une épaisseur comprise entre 50 μΐη et 1000 μΐτι, de préférence entre 100 μΐη et 800 μΐη.  13. Sheet of glass according to claim 12, characterized in that it has a thickness between 50 μΐη and 1000 μΐτι, preferably between 100 μΐη and 800 μΐη.
14. Feuille de verre selon la revendication 12 ou 13, caractérisée par le fait que la structure du textile de verre est visible par transparence à l'œil nu.  14. Glass sheet according to claim 12 or 13, characterized in that the structure of the glass textile is visible by transparency to the naked eye.
EP13795836.9A 2012-10-29 2013-10-28 Method for the production of thin sheet glass Withdrawn EP2911988A1 (en)

Applications Claiming Priority (2)

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FR1260293A FR2997392B1 (en) 2012-10-29 2012-10-29 METHOD FOR MANUFACTURING THIN GLASS
PCT/FR2013/052576 WO2014068237A1 (en) 2012-10-29 2013-10-28 Method for the production of thin sheet glass

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CN (2) CN104822633A (en)
BR (2) BR112015008672A2 (en)
CA (2) CA2888582A1 (en)
FR (1) FR2997392B1 (en)
IN (1) IN2015DN03267A (en)
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KR102295235B1 (en) 2020-04-08 2021-08-30 선문대학교 산학협력단 Method for manufacturing thin glass plate

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IN2015DN03267A (en) 2015-10-09
EP2911987A1 (en) 2015-09-02
JP2015536292A (en) 2015-12-21
BR112015008674A2 (en) 2017-07-04
CN104822634A (en) 2015-08-05
CA2888582A1 (en) 2014-05-08
CN104822633A (en) 2015-08-05
CA2888580A1 (en) 2014-05-08
KR20150080496A (en) 2015-07-09
FR2997392B1 (en) 2015-06-26
KR20150080497A (en) 2015-07-09
BR112015008672A2 (en) 2017-07-04
US20150291472A1 (en) 2015-10-15
MX2015005326A (en) 2015-07-14
RU2015120330A (en) 2016-12-20
FR2997392A1 (en) 2014-05-02
RU2015120284A (en) 2016-12-20
JP2015536293A (en) 2015-12-21
WO2014068237A1 (en) 2014-05-08
EP2911987B1 (en) 2017-03-29
US20150307394A1 (en) 2015-10-29
WO2014068233A1 (en) 2014-05-08
MX2015005325A (en) 2015-07-14

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