• 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 method of manufacturing flat glass comprising the following successive steps (a) the application of a layer of a glass frit to a glass textile, the glass of the sinter and the textile having essentially the same composition, (b) heating the glass fabric carrying the glass frit layer to a temperature T> TL - 20 ° C, TL being the Littleton temperature of the glass frit, for a time sufficient to convert the glass frit layer of frit in an enamel layer of the same composition as the glass textile, and (c) cooling of the glass textile, impregnated with enamel or having an enamel layer, obtained in step (b) , so as to obtain a glass sheet. It also relates to a glass sheet that can be obtained by this method
    公开号:FR3020361A1
    申请号:FR1453837
    申请日:2014-04-28
    公开日:2015-10-30
    发明作者:Eric Jarniaud；Pierre Olivier Petit；Benjamin Blanchard
    申请人:Saint Gobain Glass France SAS；Saint Gobain Adfors SAS；Compagnie de Saint Gobain SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a novel process for manufacturing flat glass, in particular thin glass sheets comprising a glass textile incorporated in a glass matrix. 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 300 lm. These glasses, manufactured by bat method or fusion draw, are available in large format or in continuous band form. The thinnest are flexible and can be rolled up. This flexibility makes it possible to use them in industrial processes that are conventionally reserved for films and sheets made of plastics, especially in roll-to-roll stages. 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. The present invention provides a replacement product for known thin and ultrathin glasses and a considerably simpler manufacturing process than the draw melting process. 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 satisfactory surface quality. They are made from inexpensive raw materials (glass textile and glass frit) available in large quantities and in different grades. 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 process 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 resulting from the melting of a glass frit applied to the textile. a temperature below the glass transition temperature of the glass. The Applicant has filed two international applications PCT / FR2013 / 052571 and PCT / FR2013 / 052576, not yet published at the time of filing of the present application, disclosing a method for manufacturing flat glass by impregnating a glass textile with a composition molten glass, the glass of the impregnating composition having a glass transition temperature and a softening temperature lower than that of the textile glass. In this way, the impregnating composition can be heated to fairly high temperatures where its viscosity is low without the mechanical strength of the textile being significantly reduced. The flat glass-type products obtained by the process, however, suffer from a relatively low transparency, due to the difference in the refractive indexes of the two types of glass, and also from a rather significant mechanical fragility that the Applicant attributes to the difference between the coefficients of thermal expansion of the two types of glass. The present invention relates to a process similar to that described in PCT / FR2013 / 052571, but distinguished from it by the fact that the glass constituting the textile and the frit used for the impregnation have essentially the same composition; which poses specific manufacturing problems but gives products of better transparency and mechanical resistance. The process of the present invention is distinguished by a great deal of flexibility. Indeed, the glass textile and the glass matrix can be chosen from a very large number of products available on the market. The process of the present invention can be carried out with equipment that requires relatively little heavy investment, which is a considerable advantage over the bat and merge draw processes.
    [0002] The present invention relates to a flat glass manufacturing process comprising the following three successive steps (a) application of a layer of a glass frit to a glass textile, the glass of the frit and the glass of the textile having essentially the same composition, (b) heating the glass textile carrying the glass frit layer to a temperature T> TL - 20 ° C, TL being the Littleton temperature of the glass frit, for a time sufficient to converting the frit layer into an enamel layer of the same composition as the glass textile, and (c) cooling the glass textile, impregnated with enamel or having an enamel layer, obtained in step (b) ), so as to obtain a glass sheet. In the present application the term "softening temperature" refers to the so-called Littleton (TL) temperature, also called Littleton Point, determined in accordance with ASTM C338. This is the temperature at which the viscosity of a fiberglass measured by this method is equal to 1066 Pa.s. The process is limited to the manufacture of a product from a glass textile and a glass frit powder having essentially the same composition. The expression "the same composition" means that both glasses contain the same ingredients - without however considering the elements present in the form of impurities (<1% by weight). The difference between the respective concentrations of the ingredients is at most 5% by weight, preferably at most 2% by weight, based on the lowest concentration. By way of example, when the glass forming the glass textile comprises 30% by weight of a given ingredient, the concentration of this same ingredient in the glass forming the frit is between 28.6 and 31.5% by weight. weight, preferably between 29.4 and 30.6% by weight. The difference in refractive index between the two glasses is preferably at most 0.02, in particular at most 0.01. The application of the glass frit composition in step (a) can be done according to known techniques such as screen printing, coating by means of a threaded rod, a doctor blade or a puller. coater film, roll coating, bar coating coating through a slot coating. Screen printing is a particularly preferred application technique because it can be implemented easily on an industrial scale and allows good control of the quantities applied.
    [0003] 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 carried out 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 cuts, tubes, folded or corrugated walls etc. 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 possible to melt the frit on a textile in a vertical position, so that the gravity is exerted parallel to the plane of the textile. When the textile is in a position which deviates too much from the vertical position, in particular in the horizontal position, it is essential to tension the glass fabric at least during the cooling step and preferably throughout the process. 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 (b) and this pulling force is preferably maintained, during step (c), at least until the stiffening of the product obtained. This tensioning of the glass textile during the glass melting / application step and the cooling step is perfectly compatible with and even necessary for the implementation of a continuous process which represents one embodiment of the invention. preferred embodiment of the present invention.
    [0004] In such a continuous process, the glass textile is a continuous strip and the steps (a), (b) and (c) are continuous steps implemented upstream downstream in the process line, the traction direction being parallel to the scroll direction of the glass textile continuous strip. The glass textile may be a nonwoven (veil), a knit 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. 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. The grammage of the glass textiles used is generally between 30 and 500 g / m 2, preferably between 80 and 400 g / m 2, and in particular between 100 and 250 g / m 2. The amount of glass applied as a glass frit composition, or glass paste, is in the range of 100 to 2000 g / m 2, preferably 200 to 1500 g / m 2.
    [0005] This amount of glass can of course be applied at one time, that is to say in a single layer or in several layers. The glass frit composition (glass paste) generally contains from 50 to 90% by weight, preferably from 65 to 85% by weight of a glass powder and from 10 to 50% by weight, preferably from 15 to 50% by weight. 35% of a binder, or medium, formed of an organic polymer dissolved in a solvent. The heating step (step (b)) then preferably comprises several temperature steps, the first step (100 ° C - 200 ° C) serving for the evaporation of the solvent, the second step (350 - 450 ° C) to the removal of the organic polymer and the third step (above 600 ° C) to the melting of the glass frit. The first two temperature stages are preferably each maintained for a time of between about 10 minutes and 1 hour, in particular between 15 and 30 minutes. The third heating step for melting the glass must be done in a time that depends on the temperature at which the melting is done. The higher this temperature, the shorter the duration must be to avoid the destruction of the film which occurs with a speed proportional to the viscosity of the glass. It is thus possible to carry out this heating by a flash heating step comprising increasing the textile temperature by several hundred degrees, typically by TL + 100 ° C., in a few seconds. Such a flash heating is particularly interesting from the perspective of a continuous industrial process and can be done for example by a laser sheet, a ramp of plasma torches, a burner ramp, or by heating elements (Joule effect, induction, microwave). After complete melting of the frit and the textile, the resulting film 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 minimum temperature at which it is necessary to heat the frit to melt is equal to TL-20 ° C. At this temperature the time required for the complete melting of the frit is however quite long, of the order of 2 hours. It is generally desirable to heat the frit-wearing fabric to higher temperatures, especially greater than or equal to the Littleton temperature, preferably temperatures of at least 10 ° C or even at least 20 ° C to the temperature of Littleton. When the textile is heated with the frit at a temperature of 10 ° C above the Littleton temperature, the time required for the melting of the frit layer is generally of the order of a few minutes. For most glasses, when the heating temperature is too high, one is confronted with the phenomenon of crystallization, also called devitrification, which significantly reduces, and sometimes undesirable, the transparency of the final product. For the glass E tested by the Applicant it was possible to limit or even avoid this crystallization by heating the textile with the frit at a temperature between TL-20 ° C and TL + 20 ° C. For other types of glass, however, the range of this optimum temperature range may be different, narrower or wider. This optimal heating range will, however, generally be centered around the Littleton temperature. The hot glass fabric emerging from step (b) preferably does not come into contact with any solid or liquid until it has cooled to a temperature at least 50 ° C, preferably at least 100 ° C. ° C at the softening temperature of the glass forming the molten glass composition. The flat glasses obtained in the examples below were prepared by a relatively simple process at atmospheric pressure. When the finished product contains a large number of non-evacuated air bubbles during melting, it may be advantageous to subject the textile with the enamel still hot under reduced pressure. 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 of the same composition. Such a flat product, or glass sheet, which can be manufactured by a process as described above is therefore also an object of the present invention. This glass sheet preferably has a thickness of between 50 μm and 1000 μm, in particular between 100 μm and 800 μm, ideally between 120 and 500 μm.
    [0006] In this glass sheet, 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 can no longer be visible due to the disappearance of the interfaces between the textile material and the enamel surrounding it. Example 1 A glass fabric E is coated with a glass paste consisting of a dispersion of glass powder E with a particle size of less than 63 μm in an organic solvent using a film-gun (bar coater) . The composition of the glass of the textile and the frit used for this example is as follows: oxide SiO 2 Al 2 O 3 CaO MgO SrO B 2 O 3 Na 2 O KO TiO 2 F Fe 2 O 3 SO 3 mass% 54.75 14.4 22.5 0.5 0.15 5 , 75 0.35 0.5 0.35 0.4 0.3 0.01 The glass textile is a glass fabric consisting of 166 warp yarns (68 tex) per 10 cm and 124 weft yarns per 10 cm. Its basis weight is 205 g / m2 and its thickness is about 170 μm.
    [0007] After coating, the coated textile is dried for 30 minutes at 120 ° C. The thickness of the dried film is 4001.im. The fabric is then attached to a refractory frame and annealed in an oven at 860 ° C for 40 minutes. After cooling to room temperature, the film shown in FIG. 1 is obtained. Its final thickness is 200 μm. The surface retains the imprint of the initial pattern of the textile and faintly diffuses the light. The film constitutes a gas-tight barrier. FIG. 2 is a sectional view by electron microscopy of the textile after coating and before firing: the grains of the coating and the fibers of the textile are distinctly visible.
    [0008] FIG. 3, also a sectional view obtained by electron microscopy, shows the structure of the film obtained after firing. It is no longer possible to distinguish between fibers and grains. The set is a gas impermeable film, with few closed pores. EXAMPLE 2 Example 1 is repeated with the same type of glass fabric E and the same glass frit E, except that the sample is larger in size (about 150 cm 2 instead of 20 cm 2 for Example 1). After coating and drying the textile coated for 30 minutes at 120 ° C, baking is carried out for 20 minutes at 870 ° C in an oven. Figure 4 shows the solidified film obtained.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. A method of manufacturing flat glass comprising the following successive steps (a) applying a layer of a glass frit to a glass textile, the glass frit and the textile having substantially the same composition, (b) heating the glass fabric carrying the glass frit layer to a temperature T> TL - 20 ° C, TL being the Littleton temperature of the glass frit, for a time sufficient to convert the frit layer to an enamel layer of the same composition as the glass textile, and (c) cooling the glass textile, impregnated with enamel or having an enamel layer, obtained in step (b), so as to get a sheet of glass. 15
    [0002]
    2. Method according to claim 1, characterized in that step (a) is carried out by screen printing, coating by means of a threaded rod, a doctor blade or a film puller, roll coating. or coating through a slot, preferably by screen printing.
    [0003]
    3. Method according to claim 1 or 2, characterized in that the heating temperature T is at least equal to TL, preferably at least equal to TL + 10 ° C.
    [0004]
    4. 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 (b) and in that this traction force is maintained during step (c) at least until the stiffening of the product obtained.
    [0005]
    5. Method according to one of the preceding claims, characterized in that the glass textile has a gramnnage between 30 and 500 g / m2, preferably between 80 and 400 g / m2, in particular between 100 and 250 g / m2.
    [0006]
    6. Method according to any one of the preceding claims, characterized in that the amount of glass applied in step (a) in the form of glass frit is in the range of 100 to 2000 g / m2, preferably from 200 to 1500 g / m2.
    [0007]
    7. 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.
    [0008]
    8. 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.
    [0009]
    9. Method according to any one of claims 1 to 7, characterized in that the glass textile is a nonwoven.
    [0010]
    10. Method according to any one of the preceding claims, characterized in that the hot glass textile leaving step (b) or the hot enamel layer exiting step (b) does not come into contact. with no solid or liquid before cooling to a temperature of at least 50 ° C, preferably at least 100 ° C to TL.
    [0011]
    11. Glass sheet capable of being manufactured by a method according to any one of the preceding claims.
    [0012]
    12. Glass sheet according to claim 11, characterized in that it has a thickness of between 50 lm and 1000 lm, preferably between 100 lm and 800 lm, in particular between 120 and 500 pm.
    [0013]
    13. Glass sheet according to claim 11 or 12, characterized in that the structure of the glass textile is visible by transparency to the naked eye.
    类似技术:
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    同族专利:
    公开号 | 公开日
    EP3137295A1|2017-03-08|
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    US20170044058A1|2017-02-16|
    CN106458740A|2017-02-22|
    FR3020361B1|2016-05-06|
    JP2017513802A|2017-06-01|
    MX2016014065A|2017-02-14|
    RU2016146221A|2018-05-29|
    WO2015166169A1|2015-11-05|
    BR112016024360A2|2017-08-15|
    KR20160145618A|2016-12-20|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US20100239816A1|2009-02-23|2010-09-23|Kinkade Jerald E|Composite building panel and method of making same|
    FR2997392A1|2012-10-29|2014-05-02|Saint Gobain|METHOD FOR MANUFACTURING THIN GLASS|
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    JP2002293577A|2001-03-28|2002-10-09|Nitto Boseki Co Ltd|Sizing material for glass fiber|JP2017530383A|2014-07-30|2017-10-12|コーニング インコーポレイテッド|High contrast glass-based writable / erasable front projection screen|
    EP2995635A1|2014-09-11|2016-03-16|Sulzer Chemtech AG|Method to minimize the transition time from one polymer grade to another polymer grade in a polymerization plant|
    RU2647710C1|2016-12-29|2018-03-19|Автономная некоммерческая организация высшего образования "Белгородский университет кооперации, экономики и права"|Method of stemalite production|
    CN109694256B|2019-01-23|2021-03-02|中山大学|Method for manufacturing ultrathin ceramic by fiber-assisted forming, finished product and application thereof|
    KR102295235B1|2020-04-08|2021-08-30|선문대학교 산학협력단|Method for manufacturing thin glass plate|
    法律状态:
    2015-04-04| PLFP| Fee payment|Year of fee payment: 2 |
    2015-10-30| PLSC| Publication of the preliminary search report|Effective date: 20151030 |
    2016-04-20| PLFP| Fee payment|Year of fee payment: 3 |
    2018-01-26| ST| Notification of lapse|Effective date: 20171229 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1453837A|FR3020361B1|2014-04-28|2014-04-28|METHOD FOR MANUFACTURING THIN GLASS|FR1453837A| FR3020361B1|2014-04-28|2014-04-28|METHOD FOR MANUFACTURING THIN GLASS|
    RU2016146221A| RU2016146221A|2014-04-28|2015-04-22|METHOD FOR MANUFACTURING THIN GLASS|
    KR1020167029711A| KR20160145618A|2014-04-28|2015-04-22|Method for manufacturing thin glass|
    US15/306,843| US20170044058A1|2014-04-28|2015-04-22|Method for manufacturing thin glass|
    JP2016564611A| JP2017513802A|2014-04-28|2015-04-22|Thin glass manufacturing method|
    PCT/FR2015/051097| WO2015166169A1|2014-04-28|2015-04-22|Method for manufacturing thin glass|
    CA2944338A| CA2944338A1|2014-04-28|2015-04-22|Method for manufacturing thin glass|
    CN201580023353.6A| CN106458740A|2014-04-28|2015-04-22|Method for manufacturing thin glass|
    EP15725785.8A| EP3137295A1|2014-04-28|2015-04-22|Method for manufacturing thin glass|
    MX2016014065A| MX2016014065A|2014-04-28|2015-04-22|Method for manufacturing thin glass.|
    BR112016024360A| BR112016024360A2|2014-04-28|2015-04-22|thin glass manufacturing process|
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