• 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:
    A method for obtaining a material comprising a textured glass substrate coated on at least one of its textured faces with a porous silica-based antireflection sol-gel coating, said method comprising the following steps a step of applying to said at least one textured face of said substrate a solution containing at least one silica precursor and at least one pore-forming agent, and then a heat treatment step for consolidating said antireflection coating, said method being such that before said step of applying the glass substrate is subjected to a preheating step so that said at least one textured face intended to be coated by said antireflection coating has a temperature in a range from at 100 ° C, especially 50 to 80 ° C, immediately before the application step.
    公开号:FR3068690A1
    申请号:FR1770729
    申请日:2017-07-07
    公开日:2019-01-11
    发明作者:Guillaume Lequippe；Xiolin PARDAL；Servane Haller
    申请人:Saint Gobain Glass France SAS；Compagnie de Saint Gobain SA；
    IPC主号:
    专利说明:

    PROCESS FOR OBTAINING A COATED TEXTURED GLASS SUBSTRATE
    AN ANTIREFLECTIVE SOL-GEL COATING.
    The invention relates to the field of materials comprising a glass substrate coated with at least one anti-reflection coating.
    It relates in particular to materials which can be used on the roofs of agricultural, horticultural or urban greenhouses.
    Glass materials intended for use as greenhouse glass must meet certain requirements in terms of optical properties and durability. Their high light transmission possible, and it must in particular be the best known for this to use extra-clear glass substrates and to coat these substrates with anti-reflective layers based on porous silica obtained by processes of the sol- gel. Due to their low refractive index, ideally close to the square root of the refractive index of the glass substrate and their high chemical durability, these layers have proved to be particularly suitable.
    Such layers are in particular described in application FR2908406.
    It turns out that the yields of crops installed in greenhouses are also improved by the use of substrates capable of diffusing light. Diffuse and homogeneous lighting optimizes plant growth. To do this, glass substrates having at least one textured face have been developed. Such substrates are for example obtained by rolling the glass, that is to say by passing the hot glass between rollers themselves textured, which come to print the glass surface and create a relief. The term "printed glass" is also used in the art.
    However, it turned out that the deposition of anti-reflective solgel layers of the type described above by applying a solution to a textured surface did not make it possible to obtain perfectly optimized optical properties, in particular for the most important textures.
    The inventors have been able to demonstrate that even if the solution was deposited homogeneously over the entire surface of the glass, the texturing of the latter induced during the drying of the capillary forces favoring a flow in the valleys of the textured structure, leading after drying to a heterogeneous layer in thickness, in which the layer is very thin, or even nonexistent at the peaks of the structure. This results in a spatial heterogeneity of the light reflection factor, and therefore a lower overall light transmission factor than if the layer were perfectly homogeneous.
    The object of the invention, which is to obviate these drawbacks, is a process for obtaining a material comprising a textured glass substrate coated on at least one of its textured faces with a coating of the soil type. anti-reflective gel based on porous silica, said process comprising the following stages:
    a step of applying to said at least one textured face of said substrate a solution containing at least one silica precursor and at least one pore-forming agent, then a heat treatment step aimed at consolidating said anti-reflective coating, said process being such that before said application step the glass substrate is subjected to a preheating step so that said at least one textured face intended to be coated with said anti-reflective coating has a temperature in a range from 30 to 100 ° C immediately before the application step.
    The glass substrate is generally in the form of plates, generally rectangular, with a thickness ranging from 1 to 10 mm, in particular from 2 to 8 mm, or even from 3 to 6 mm. The lateral dimensions of the plates typically range from 0.5 to 3 m.
    The glass substrate preferably consists of a glass of the soda-lime-calcium type. Other types of glass can however be used, such as borosilicate or aluminosilicate glasses. The glass substrate is preferably an extra-clear glass, in the sense that the total mass content of iron oxide is in a range from 10 to 200 ppm, in particular from 20 to 150 ppm. The light transmission factor within the meaning of standard EN 410 of the glass substrate is advantageously at least 90%, even 91%.
    By “textured face”, it is meant that the face in question presents a relief, composed of a succession of peaks and valleys. This relief can be periodic or random.
    At least one textured face of the substrate intended to be coated with the anti-reflective coating preferably has a profile such that, within the meaning of standard ISO 4287: 1997:
    the parameter Rz is included in a range from 18 to 200 pm, in particular from 20 to 150 pm, and in particular from 50 to 120 pm, and
    - the RSm parameter is included in a range from 500 to 2500 pm, in particular from 600 to 2000 pm.
    These values are obtained using 25 µm filters and 8 mm Xc filters.
    Texturing is capable of creating a blur, and therefore of diffusing light. The glass substrate advantageously has a haze of at least 20%, especially 40% and even 50% or 70%, even 80%. In general, a higher value of the parameter Rz is associated with a higher blurring. The blur is measured according to ISO 14782: 1999.
    The glass substrate may have a single textured face, or two textured faces.
    The textured glass substrate is preferably obtained by rolling the glass. This technique consists, at the exit of the melting furnace, during the shaping of the glass, in passing the hot glass between two rollers, generally metallic, at least one of which is textured, that is to say presents a relief. The hot glass is then printed by the textured roller, the relief thus created being preserved during the cooling of the glass.
    Other texturing methods are possible, such as chemical or mechanical attacks: acid attack, in particular hydrofluoric, or sandblasting, by projection onto the surface of the glass of abrasive particles. These methods are, however, more expensive and less environmentally friendly.
    The coating is of the sol-gel type, that is to say obtained by a sol-gel process.
    A sol-gel process typically includes:
    the formation of a "sol", that is to say of a solution containing at least one precursor, here of silica,
    - applying this solution to the surface to be coated,
    - consolidation or densification of the coating by means of heat treatment.
    The solution preferably contains a dry extract of at most 10%, especially 5% by weight, and generally at least 1% by weight.
    The solvent for the solution is preferably chosen from water, organic solvents, and mixtures of water and organic solvent. The organic solvents are preferably chosen from alcohols (for example isopropanol, propanol, ethanol, etc.) and acetone. The term "solvent" is used here in its generic sense, so that the solvent can consist of a mixture of solvents.
    The solution is preferably aqueous, in the sense that the solvent of the solution contains at least 50% by weight of water, or even 60%, and even 70% or 80% or even 90% or 95%. The solvent is even preferably completely aqueous, in the sense that it consists of water. The use of aqueous solutions or at least predominantly aqueous has indeed advantages in terms of environment, industrial hygiene, cost, but also durability of the layer obtained. It also turns out that the advantages linked to the invention in terms of thickness uniformity are all the more important the higher the amount of water in the solvent.
    The anti-reflective coating is based on silica. The silica content of the coating is preferably at least
    60% by weight, especially 70% and even 80% or 90% by weight. The coating advantageously consists of silica.
    The silica precursor is preferably a compound chosen from alkoxides and silicon halides, for example tetraethyl orthosilicate (TEOS). The silica precursor can also be a product of chemical reactions occurring between these compounds and other constituents of the solution, for example water when the solvent contains it. These compounds are in fact capable of hydrolyzing at least partially during the formation of the solution, therefore before application.
    The blowing agent is preferably solid, the choice of its size making it possible to vary the size of the pores. The blowing agent is preferably particulate, in particular of substantially spherical shape, for example in the form of beads, hollow or solid. The blowing agent is preferably organic in nature. By way of example, the blowing agent comprises polymeric beads, in particular of a polymer chosen from polymethyl methacrylate (PMMA), methyl (meth) acrylate / (meth) acrylic acid copolymers, polycarbonates, polyesters , polystyrene.
    The solution to be applied is preferably acidic. Its pH is preferably between 0 and 5, in particular between 1 and 3.
    In addition to the silica precursor and the blowing agent, the solution can include other components, such as pH regulating agents, surfactants, etc.
    The application of the solution is preferably carried out by coating by means of at least one roller, a technique also called “roll coating”, which allows precise control of the quantity of solution deposited as well as the spatial homogeneity of the deposit.
    According to this technique, the glass substrate is preferably made to pass under a metering roller and an applicator roller in quasi contact with one another and in rotation in the same direction or in the opposite direction, the applicator roller being in contact with the face of the substrate to be coated, and the solution to be applied being poured from above between these two rollers. The solution, passing between the metering roller and the applicator roller, is deposited on the surface of the latter, then is transferred to the face to be coated.
    Other known application techniques can also be used, for example spraying, soaking, curtain techniques, etc.
    Immediately after the application step, before the heat treatment step, the method according to the invention preferably comprises a drying step. This step is intended to accelerate the evaporation of the solvent contained in the coating. It can be implemented by any known means, for example by blowing hot air. The air temperature is then preferably between 50 and 160 ° C, and the drying time preferably between 5 and 60 seconds.
    The heat treatment step consolidates the anti-reflective coating. During this stage, the blowing agents are also eliminated, creating a porosity within the coating, thus making it possible to lower its refractive index.
    The heat treatment preferably involves bringing the coating to a temperature of at least 400 ° C., in particular 500 ° C.
    The heat treatment is preferably a glass toughening treatment. Tempering the glass consists of reheating the glass to a temperature generally above 600 ° C. and then cooling it quickly, generally by means of nozzles emitting cold air. This rapid cooling makes it possible to create compressive stresses on the surface of the glass substrate, and therefore to reinforce its mechanical and impact resistance.
    The anti-reflective coating preferably comprises closed pores having a smaller characteristic dimension which is advantageously, on average, at least 20 nm, in particular 40 nm, or even 50 nm and at most 1 pm, in particular 500 nm, even 100 nm. The pore distribution is preferably substantially homogeneous in thickness. The volume proportion of the pores in the coating is preferably between 10 and 90%, in particular between 20 and 80%, or even between 30 and 70%.
    The anti-reflective coating preferably has an average thickness ranging from 10 nm to 10 μm, in particular from 20 nm to 1 μm, or even from 30 to 300 nm or from 50 to 200 nm.
    The anti-reflective coating advantageously has a refractive index for a wavelength of 600 nm of at most 1.40, in particular 1.30.
    The anti-reflective coating may be the only coating carried by the glass substrate. Alternatively, other coatings may be present on the same face or on another face of the substrate. In particular, it is advantageous to interpose between the glass substrate and the anti-reflective coating a sublayer containing silicon, oxygen, and optionally nitrogen and / or carbon, such as a layer of silica , oxycarbide or silicon oxynitride. Such an underlayer is particularly useful when the glass contains alkaline ions because it is able to form a barrier to said ions. A non-porous silica sublayer having a refractive index between 1.35 and 1.45 has also been found to be useful in increasing the light transmission of the material. Such sublayers preferably have a thickness in a range from 10 to 200 nm, in particular from 80 to 120 nm. They can be deposited by any type of process, for example of the sol-gel type, chemical vapor deposition (CVD), sputtering, etc.
    Without the reason being known, it turned out that the preheating step made it possible to homogenize the thickness of the anti-reflective coating. This results in a gain in terms of hemispherical light transmission of the material.
    The preheating step is carried out in such a way that the at least one textured face intended to be coated with said anti-reflective coating has a temperature ranging from 30 to 100 ° C, in particular 50 to 80 ° C immediately before the 'application step. By "immediately" is preferably meant that the textured face to be coated has a temperature in the aforementioned range at most 5 seconds, in particular 3 seconds, or even 1 second before the start of the application of the solution.
    The temperature of the surface to be coated can be measured by any known means, for example by means of a pyrometer.
    The preheating step is preferably carried out by radiation, for example by means of infrared lamps or microwave radiation or also by convection, for example by blowing hot air.
    The method according to the invention is generally continuous, and in particular implements the running of the glass substrate successively in a preheating device, for example an oven, then in a device for applying the solution, for example by means of 'at least one roller, then in a heat treatment device, for example a quenching oven. The preheating device is preferably located immediately upstream of the application device, so as to be able to best control the temperature of the surface to be coated before the start of the application. A drying device is advantageously interposed between the application device and the heat treatment device. Preferably, the drying device employs preheated air at the heat treatment device.
    The material obtained according to the invention is characterized in particular by the fact that the anti-reflective coating is particularly uniform in thickness.
    An object of the invention is therefore also a material, in particular capable of being obtained by the method according to the invention, which comprises a textured glass substrate coated on at least one of its textured faces with a coating of the soil type. anti-reflective gel based on porous silica. Said textured face has a relief composed of a succession of peaks and valleys, and the local thickness of the anti-reflective coating at the peaks is at least 60 nm, in particular 80 nm and even 100 nm, and the local thickness of the anti-reflective coating at the level of the valleys is at most 700 nm, in particular 600 nm and even 500 nm.
    Preferably, the value of the local thickness of the anti-reflective coating at the level of said peaks is at least 40%, in particular 50 or 60% of the value of the local thickness of the anti-reflective coating at the level of said valleys. Observation by microscopy, in particular using a scanning electron microscope, in particular carried out on the edge of the material, makes it possible to measure these local thicknesses.
    As indicated above, the glass substrate can have a single textured face or two textured faces. At least one textured side is coated with the anti-reflective coating of the sol-gel type. The other face of the substrate, whether textured or not, may or may not be coated with an anti-reflective coating, of the sol-gel type or not. All combinations of characteristics are possible here.
    The material preferably has a light transmission factor, within the meaning of standard EN410 of at least 92%, in particular 93% and even 94%. When both sides of the substrate are coated with an anti-reflective coating, the light transmission factor can even
    to be at least 96% , especially 97% or 98%. The coating anti reflection allows, when is filed sure one side of substrate, to increase the factor of
    light transmission of at least 1%, especially 2% and even 3%. This is an absolute, not a relative increase.
    The characteristics relating in particular to the substrate and to the anti-reflective coating presented above during the description of the process according to the invention also apply to the material according to the invention.
    Another object of the invention is a greenhouse, in particular an agricultural, horticultural or urban greenhouse, comprising at least one material according to the invention. The material is preferably integrated into the roof of the greenhouse. The textured side of the material which is coated with the anti-reflective coating can be turned to the interior or exterior side of the greenhouse.
    Other applications of the material according to the invention are also possible. The material according to the invention can for example be used as the front face of a photovoltaic cell.
    The examples which follow illustrate the invention in a nonlimiting manner.
    Two glass substrates having a textured face were coated with an anti-reflective sol-gel coating as described in application FR 2 908 406, using
    a solution totally aqueous containing TEOS like precursor of silica and a blowing agent form of polymeric beads.Both substrates, called substrate A and substrate B present to the state no coated characteristics in
    terms of surface condition and optical properties given in table 1 below. The roughness parameters Rz and RSm are defined according to ISO 4287: 1997, blurring according to ISO 14782: 1999 and the light transmission factor (TL) according to EN 410.
    substratum Rz (pm) RSm (pm) Blurry (%) TL (%) AT 72 1530 50 91 B 100 1800 55 91
    Table 1
    In a comparative example, the glass substrates were not preheated before application of the solution. In an example according to the invention, the glass substrates were preheated using infrared lamps, so that the temperature of the substrate was 70 ° C. immediately before application of the solution. This temperature was measured using a pyrometer.
    Table 2 below presents, for each of the examples, the gain in light transmission obtained. This absolute gain, noted ATL, is expressed in%.
    AT B ATL (%) - comparison 1.3 0.9 ATL (%) - invention 1.8 1.4
    Table 2
    It can therefore be seen that the preheating step has made it possible to improve the anti-reflection efficiency of the coating, so that the material has a higher light transmission. The gain linked to the preheating step is of the order of 0.5% absolute.
    权利要求:
    Claims (1)
    [1" id="c-fr-0001]
    1. A method for obtaining a material comprising a textured glass substrate coated on at least one of its textured faces with an anti-reflective sol-gel coating based on porous silica, said method comprising the following steps:
    a step of applying to said at least one textured face of said substrate a solution containing at least one silica precursor and at least one pore-forming agent, then
    a heat treatment step aimed at consolidating said anti-reflective coating, said method being such that before said application step, the glass substrate is subjected to a preheating step so that said at least one textured face intended to be coated with said anti-reflective coating has a temperature in a range from 30 to 100 ° C, especially from 50 to 80 ° C, immediately before the application step.
    2. Method according to claim 1 such as the solution is aqueous. 3. Process according to 1 'a of the claims previous s, such that at least a face textured of the substrate of glass intended to be coated through the coating
    anti-reflective has a profile such that, within the meaning of ISO 4287: 1997:
    The parameter Rz is included in a range from 18 to 200 pm, in particular from 20 to 150 pm, and in particular from 50 to 120 pm, and
    - The RSm parameter is included in a range from 500 to 2500 pm, in particular from 600 to 2000 pm.
    4. Process according to one of the claims
    above, such that the glass substrate has a haze of at least 20%, in particular 40% and even 50%.
    5. Method according to one of the preceding claims, such that the light transmission factor within the meaning of standard EN 410 of the glass substrate is at least 90%, or even 91%.
    6. Process according to one of the claims previous, such that the application of the solution is
    produced by coating with at least one roller.
    7. Process according to one of the claims
    above, such that the silica precursor is a compound chosen from alkoxides and silicon halides.
    8. Process according to one of the claims previous, such that at least one blowing agent is
    organic in nature, in particular comprises polymer beads, in particular of a polymer chosen from
    polymethyl methyl, copolymers
    methyl (meth) acrylate / (meth) acrylic acid, polycarbonates, polyesters, polystyrene.
    9. Process according to one of the claims previous, such that the preheating step is carried out by radiation, in particular by means of infrared lamps,
    or by convection, in particular by blowing hot air.
    10. Process according to one of the claims previous, such that heat treatment is a
    tempering treatment of glass.
    11. Process according to one of the claims previous, which includes immediately after the step
    application and before the heat treatment step, a drying step.
    12. Process according to one of the claims previous, such that the anti-reflective coating has a
    average thickness in a range from 10 nm to 10 pm, in particular from 20 nm to 1 pm.
    13. Material, in particular capable of being obtained according to the method of any one of claims 1 to
    5 12, comprising a textured glass substrate coated on at least one of its textured faces with an anti-reflective sol-gel type coating based on porous silica, said textured face having a relief composed of a succession of peaks and valleys , said material being such that the local thickness of the anti-reflective coating at the peaks is at least 60 nm, in particular 80 nm and even 100 nm,
    and 1'épaisseur local from coating anti reflection at the level of the east valleys at most 700 nm, including 600 nm and even 500 nm. 1514. Greenhouse comprising at least a material according to
    previous claim.
    类似技术:
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    同族专利:
    公开号 | 公开日
    CN110809566A|2020-02-18|
    WO2019008282A2|2019-01-10|
    US20200131082A1|2020-04-30|
    EP3649091A2|2020-05-13|
    KR20200027957A|2020-03-13|
    RU2020102711A|2021-08-10|
    EP3649091B1|2022-02-16|
    WO2019008282A3|2019-02-28|
    RU2020102711A3|2021-11-02|
    FR3068690B1|2019-08-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4694218A|1984-05-04|1987-09-15|Cotek Company|Non-glaze coating for a cathode ray tube|
    WO2011018590A1|2009-08-13|2011-02-17|Essilor International |Method for manufacturing a substrate coated with mesoporous antistatic film, and use thereof in ophthalmic optics|
    FR2908406B1|2006-11-14|2012-08-24|Saint Gobain|POROUS LAYER, METHOD FOR MANUFACTURING THE SAME, AND APPLICATIONS THEREOF|
    FR2941447B1|2009-01-23|2012-04-06|Saint Gobain|TRANSPARENT GLASS SUBSTRATE AND METHOD FOR MANUFACTURING SUCH A SUBSTRATE.|
    JP2014507686A|2011-02-11|2014-03-27|ディーエスエムアイピーアセッツビー．ブイ．|Method for depositing an antireflective layer on a substrate|
    FR2995245B1|2012-09-10|2015-05-15|Saint Gobain|DECORATIVE GLAZING WITH REFLECTIVE LAYER DEPOSITED ON A TEXTURED SUBSTRATE|WO2021182485A1|2020-03-11|2021-09-16|日本板硝子株式会社|Greenhouse, and coating-film-attached glass plate|
    WO2022043186A1|2020-08-28|2022-03-03|Agc Glass Europe|Improved greenhouse glazing|
    CN112408763B|2020-11-23|2021-11-05|徐州创合新材料科技有限公司|Toughened glass heat-insulating coating and preparation method thereof|
    法律状态:
    2019-01-11| PLSC| Publication of the preliminary search report|Effective date: 20190111 |
    2019-07-18| PLFP| Fee payment|Year of fee payment: 3 |
    2020-07-24| PLFP| Fee payment|Year of fee payment: 4 |
    2021-07-29| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1770729A|FR3068690B1|2017-07-07|2017-07-07|METHOD FOR OBTAINING A TEXTURE GLASS SUBSTRATE COATED WITH AN ANTIREFLET SOL-GEL COATING.|
    FR1770729|2017-07-07|FR1770729A| FR3068690B1|2017-07-07|2017-07-07|METHOD FOR OBTAINING A TEXTURE GLASS SUBSTRATE COATED WITH AN ANTIREFLET SOL-GEL COATING.|
    RU2020102711A| RU2020102711A3|2017-07-07|2018-07-05|
    KR1020207002569A| KR20200027957A|2017-07-07|2018-07-05|Method for preparing a textured glass substrate coated with an anti-reflective sol-gel-type coating|
    PCT/FR2018/051685| WO2019008282A2|2017-07-07|2018-07-05|Method for producing a textured glass substrate coated with an anti-reflective sol-gel-type coating|
    US16/629,149| US20200131082A1|2017-07-07|2018-07-05|Process for obtaining a textured glass substrate coated with an antireflective coating of sol-gel type|
    CN201880045509.4A| CN110809566A|2017-07-07|2018-07-05|Method for obtaining a textured glass substrate coated with an anti-reflection coating of the sol-gel type|
    EP18773507.1A| EP3649091B1|2017-07-07|2018-07-05|Method for producing a textured glass substrate coated with an anti-reflective sol-gel-type coating|
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