• 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 transport vehicle glazing comprising, on its surface intended to be exposed to the external atmosphere, at least in a zone not swept by the wipers, a mineral oxide layer of 0.1 to 20 μm thick, of which 30 to 90% of the volume consists of open pores of 20 to 300 nm, distributed homogeneously throughout the thickness of the layer, and which are almost all connected to each other the outer and inner surface of the layer being functionalized with a perfluoroalkyl or alkyl functional compound, then saturated with a hydrophobic oil which impregnates the functionalized porous layer and forms a film on the surface thereof, said at least one zone being vis-à-vis a detection device such as security camera / obstacle detection / anti-collision, or the like, placed inside the vehicle, in particular on the face of the glazing; a method for manufacturing it and its application as a transport vehicle windshield.
    公开号:FR3040700A1
    申请号:FR1558264
    申请日:2015-09-07
    公开日:2017-03-10
    发明作者:Barbara Brudieu；Francois Guillemot；Jeremie Teisseire
    申请人:Saint Gobain Glass France SAS；
    IPC主号:
    专利说明:

    The invention relates to a glazing of a transport vehicle through which operates a detection apparatus such as security camera / obstacle detection / anti-collision. , or the like, placed inside the vehicle, in particular on the face of the glazing.
    The inventors have sought to ensure a maximum and lasting cleanliness of the face of the glazing intended to be exposed to the outside atmosphere, in its zone vis-à-vis the detection apparatus. They searched for functional systems with water-repellent properties (low hysteresis, that is, a small difference between the angle of advance and the angle of retreat of a drop of water on the inclined substrate, and angle of high contact) thanks to a perfectly flat hydrophobic coating. Thus, we aim to obtain a glazing with high and durable transparency, on the outer surface of which slides liquids such as water which implies anti-dust and anti-fogging properties.
    This object is achieved by the invention which relates to a transport vehicle glazing comprising, on its surface intended to be exposed to the outside atmosphere, at least in a zone not swept by the wipers, a layer of mineral oxide 0.1 to 20 μm thick, 30 to 90% of the volume of which consist of open pores of 20 to 300 nm, distributed homogeneously throughout the thickness of the layer, and which for their quasi-uniformity are connected to each other, the outer and inner surface of the layer being functionalized with a perfluoroalkyl or alkyl functional compound, then saturated with a hydrophobic oil which impregnates the functionalized porous layer and forms a film on the surface thereof, said at least one zone being vis-à-vis a detection device such as security camera / obstacle detection / anti-collision, or the like, placed inside the vehicle, in particular on the face of the window ge.
    By "internal surface" of the layer is meant here the surface of the pores. The hydrophobic oil comprises a fluorinated oil or a non-fluorinated silicone. It impregnates the porous silica layer and forms a film on the surface thereof by virtue of the affinity (non-covalent bonds) with the perfluoroalkyl functional compound or alkyl grafted on the surface of the pores (this grafting modifies the surface tension (internal and external) of the mineral oxide layer). This leads to a hydrophobic flat layer of liquid and / or semi-liquid hemi-liquid nature. The porous layer makes it possible to maintain the hydrophobic oil that is durable because of its impregnation in the porous layer (a hydrophobic oil on glass is not as effective in terms of sliding property).
    Surprisingly the complex coating of the glazing of the invention is durable and compatible with the demanding conditions of use of a motor vehicle windshield, for example, ensuring the durability of the optimal operation of an obstacle detection camera or similar.
    The outer surface of the glazing has excellent water sliding properties, as well as dust removal by water sliding, and anti-fogging.
    The manufacture of the complex coating according to the invention is feasible over large areas, and its parameters such as fraction of pore volume, adhesion ... are easily controllable.
    According to other preferred characteristics of the glazing of the invention: the layer is made of silica; the porous layer being non-rough and made of silica, its refractive index is low (from about 1.15 to 1.30 at a wavelength of 600 nm) which makes it possible to have a transparent system on glass ( no diffraction or scattering of light); at least 40, preferably 50% of the volume of the layer consist of pores; at most 80% of the volume of the layer consist of pores; the pore dimensions are at least 30, preferably 40 and particularly preferably 50 nm; the pore dimensions are at most 200 nm; the hydrophobic oil is chosen from perfluorinated hydrocarbons or organic silicones, for example elastomers, perfluoropolyethers, perfluoroalkylethers and perfluorocycloethers, tertiary perfluoroalkylamines, perfluoroalkylsulfides and perfluoroalkylsulfoxides, perfluoroalkylphosphines and their oxidation products, perfluorinated carboxylic acids, sulphonic acids and phosphonic acids; fluorinated silanes, fluorinated silanes, alone or as a mixture of several of them. The subject of the invention is also a method for manufacturing a glazing unit as described above, characterized in that it comprises the operations consisting successively of depositing on a glass substrate a liquid composition of porogenic agent and precursor (s). ) of mineral oxide, - calcining the assembly obtained so as to eliminate the pore-forming agent and form a condensed porous layer on the substrate, - grafting on the outer and inner surface of the porous layer a perfluoroalkyl or alkyl functional compound, and then pouring an excess hydrophobic oil onto the inclined holding substrate to remove excess oil from the substrate.
    According to preferred features of this process: the inorganic oxide is silica and the silica precursors jointly used are glycidoxypropyltrimethoxysilane (GLYMO) and tetraethoxysilane (TEOS); the use of GLYMO as a precursor makes it possible to obtain relatively thick layers (thicknesses greater than 1.5 μm) free of cracks with a relatively high pore volume, greater than 50%; the blowing agent is chosen from a latex of acrylic particles such as polymethylmethacrylate (PMMA), or a (meth) acrylic polymer emulsion; the liquid composition of porogenic agent and precursor (s) of inorganic oxide is deposited on the substrate by roll, spraying, dipping, screen printing (with rheology adjustment) or printing for example by ink jet; the perfluoroalkyl-functional compound has the general formula (I) F3C- (CF2) m- (CH2) n -SiX3-pRp in which - m = 0 to 15, preferably 5 to 11 and particularly preferably at most 9 ; n = 1 to 5, preferably n = 2; p = 0, 1 or 2, preferably 0 or 1 and particularly preferably 0; R is an alkyl group or a hydrogen atom; and X is a hydrolyzable group such as hydroxy or alkoxy, especially ethoxy, methoxy, or halide; or consists of a perfluoropolyethersilane of the type represented by the general formula (II)
    or by the general formula (NI)
    in which: - m = 2 to 30 - n = 1 to 3, preferably n = 1 - p = 0, 1 or 2, preferably 0 or 1, and particularly preferably 0; R is an alkyl group or a hydrogen atom; and - X is a hydrolyzable group such as hydroxy or alkoxy, especially ethoxy, methoxy, or halide; or alternatively consists of a perfluoropolyether carrying a two-ended alkoxysilane group, in particular such as marketed under the trademark Fluorolink® by the company Solvay; prior to grafting the perfluoroalkyl or alkyl functional compound, the outer and inner surface of the porous layer is hydrophilic, and the perfluoroalkyl or alkyl functional graft precursor is hydrolyzed so as to condense with the surface of the layer to obtain grafting. .
    Another object of the invention is the application of a glazing as described above, as windshield of land transport vehicle, including automobile or rail, air or aquatic. The invention will be better understood in the light of the following example embodiment.
    Example
    A solution of glycidoxypropyltrimethoxysilane (GLYMO) is prepared by mixing 10 g of GLYMO and 2.25 g of HCl solution at pH = 2, with stirring at room temperature for approximately 2 hours.
    A solution of tetraethoxysilane (TEOS) is prepared by mixing 4 g of TEOS and 6 g of HCl solution at pH = 2, with stirring at room temperature for approximately 2 hours.
    A GLYMO-TEOS sol is prepared by mixing 1 part of GLYMO sol with 2 parts of TEOS sol (by mass).
    The solution to be deposited is prepared by mixing 0.98 g of GLYMO-TEOS sol prepared above, 0.59 g of methacrylic polymer emulsion marketed under the trademark NeoCryl® XK-52 by the company DSM, 3,4 g of HCl solution at pH = 2, and 0.5% by weight of fluorinated surfactant marketed under the registered trademark Novec® FC-4430 by the company 3M.
    This solution is rolled onto a 10 cm × 10 cm and 4 mm thick silicosodocalcic float glass sample. The sample is calcined at 450 ° C. for the purpose of degrading the porogen (NeoCryl® XK-52). A condensed porous silica layer of 1.7 μm in thickness, free of crack or cracking, of 60% porosity, with pores of 60 nm which are almost all connected to each other throughout the thickness of coating.
    A mixture of 213 μl of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (hereinafter referred to as SiF7) corresponding to the formula F3C- (CF2) 7- (CH2) 2 -Si (OC2H5) 3, 9 g is then prepared. isopropanol (IPA) and 1 g of 0.1 N HCl. This mixture is at pH = 1. SiF7 is hydrolyzed therein, i.e., each of the three ethoxy groups is replaced by an OH hydroxy group.
    The surface of the condensed porous silica layer prepared above is rendered hydrophilic by UV-ozone treatment for 60 minutes at 50 ° C, and then the hydrolysed SiF7 mixture prepared above is crumpled (i.e. deposited by means of a soaked cloth) on the surface of the hydrophilic porous layer so that the Si-OH SiF7 groups condense with those of the porous layer forming Si-O-Si bonds. Instead of scraping, a spray can also be used to deposit the hydrolysed SiF7 mixture. The sample is then annealed at 150 ° C for 30 to 60 minutes.
    On the porous layer thus functionalized with SiF7, an excess perfluoropolyether oil of formula F- (CFCF3-CF2-O) n-CF2CF3 is cast in excess with n between 10 and 60, of viscosity 12.6 cP, marketed by Du Pont company under the registered trademark Krytox GL 100 ®. The sample is held inclined to remove excess oil from the substrate. The amount of oil retained by it is at least equal to 0.5 ml / cm 2.
    A drop of water on the surface of the porous layer + SiF7 + Krytox® coating does not spread out and slides even when the sample is flat. The coating is hydrophobic and the fluorinated liquid, immiscible with water prevents any attachment of the drop by capillary force. A slight inclination (5 °) is enough for the drop to slip out of the sample without leaving a trace.
    The slippery coating is durable in two points: - The fluorinated oil remains impregnated for a long time in the porous layer although it is fluid and that it is undoubtedly carried in small quantity by the drops of water sliding on the surface. A volume of 200ml water dripped at the same point on the surface of the sample, does not reduce the slippery properties. - A cleaning of the coating or a very long use implies a gradual withdrawal of the oil. Nevertheless, it can be reapplied easily to the surface of the sample (coated with the porous layer functionalized with residual oil) to enable it to recover performance equivalent to the first use.
    In addition, this slippery property gives the coating anti-dust and antifreeze functions.
    The sliding coating with a macroporous layer is very interesting for the glazing where transparency is required and where anti-fingerprint, anti-dust and / or antifreeze functions are desired. It is particularly interesting, in the context of the invention, to coat the area of the windshield of cars behind which is the obstacle detection camera (more commonly used by car manufacturers), or equivalent.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    1. Transport vehicle glazing comprising, on its surface intended to be exposed to the external atmosphere, at least in an area not swept by the wipers, a mineral oxide layer of 0.1 to 20 μm. thickness, of which 30 to 90% of the volume consists of open pores of 20 to 300 nm, distributed homogeneously throughout the thickness of the layer, and which are almost all connected to each other, the outer surface and internally of the layer being functionalized with a perfluoroalkyl or alkyl functional compound, then saturated with a hydrophobic oil which impregnates the functionalized porous layer and forms a film on the surface thereof, said at least one zone being vis-à-vis -vis a detection device such as security camera / obstacle detection / anti-collision, or the like, placed inside the vehicle, in particular on the face of the glazing.
    [2" id="c-fr-0002]
    2. Glazing according to claim 1, characterized in that the layer is silica.
    [3" id="c-fr-0003]
    3. Glazing according to one of the preceding claims, characterized in that at least 40, preferably 50% of the volume of the layer consist of pores.
    [4" id="c-fr-0004]
    4. Glazing according to one of the preceding claims, characterized in that at most 80% of the volume of the layer consist of pores.
    [5" id="c-fr-0005]
    5. Glazing according to one of the preceding claims, characterized in that the pore size is at least 30, preferably 40 and particularly preferably 50 nm.
    [6" id="c-fr-0006]
    6. Glazing according to one of the preceding claims, characterized in that the pore size is at most 200 nm.
    [7" id="c-fr-0007]
    7. Glazing according to one of the preceding claims, characterized in that the hydrophobic oil is chosen from perfluorinated hydrocarbons or organic silicones, for example elastomers, perfluoropolyethers, perfluoroalkylethers and perfluorocycloethers, tertiary perfluoroalkylamines, perfluoroalkylsulfides and perfluoroalkylsulfoxides, perfluoroalkylphosphines and their oxidation products, perfluorinated carboxylic acids, fluorinated sulfonic and phosphonic acids, fluorinated silanes, alone or as a mixture of several of them.
    [8" id="c-fr-0008]
    8. A method of manufacturing a glazing according to one of the preceding claims, characterized in that it comprises the successive operations of - depositing on a glass substrate a liquid composition of pore-forming agent and precursor (s) mineral oxide, - calcining the assembly obtained so as to eliminate the pore-forming agent and form a condensed porous layer on the substrate, - grafting on the outer and inner surface of the porous layer a perfluoroalkyl or alkyl-functional compound, then - casting an excess hydrophobic oil on the inclined holding substrate to remove excess oil from the substrate.
    [9" id="c-fr-0009]
    9. The method of claim 8, characterized in that the inorganic oxide is silica and the silica precursors jointly implemented are glycidoxypropyltrimethoxysilane and tetraethoxysilane.
    [10" id="c-fr-0010]
    10. The method of claim 8 or 9, characterized in that the blowing agent is selected from a latex of acrylic particles such as polymethyl methacrylate, or a (meth) acrylic polymer emulsion.
    [11" id="c-fr-0011]
    11. Method according to one of claims 8 to 10, characterized in that the liquid composition of porogen and precursor (s) of inorganic oxide is deposited on the substrate by roller, spraying, dipping, screen printing (with adjustment rheology) or inkjet printing.
    [12" id="c-fr-0012]
    12. Method according to one of claims 8 to 11, characterized in that the perfluoroalkyl compound has the general formula (I) F3C- (CF2) m- (CH2) n -SiX3-pRp in which - m = 0 at 15, preferably 5 to 11 and particularly preferably at most 9; n = 1 to 5, preferably n = 2; p = 0, 1 or 2, preferably 0 or 1 and particularly preferably 0; R is an alkyl group or a hydrogen atom; and X is a hydrolyzable group such as hydroxy or alkoxy, especially ethoxy, methoxy, or halide; or consists of a perfluoropolyethersilane of the type represented by the general formula (II)

    or by the general formula (NI)

    in which: - m = 2 to 30 - n = 1 to 3, preferably n = 1 - p = 0, 1 or 2, preferably 0 or 1, and particularly preferably 0; R is an alkyl group or a hydrogen atom; and - X is a hydrolyzable group such as hydroxy or alkoxy, especially ethoxy, methoxy, or halide; or else it consists of a perfluoropolyether carrying a two-ended alkoxysilane group.
    [13" id="c-fr-0013]
    13. Method according to one of claims 8 to 12, characterized in that prior to grafting the perfluoroalkyl compound or alkyl, the outer and inner surface of the porous layer is hydrophilic, and in that the functional graft precursor perfluoroalkyl or alkyl is hydrolyzed to condense with the surface of the layer to obtain grafting.
    [14" id="c-fr-0014]
    14. Application of a glazing according to one of claims 1 to 7, as windshield of land transport vehicle, including automobile or rail, air or water.
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    引用文献:
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    US10221321B2|2015-08-28|2019-03-05|Battelle Memorial Institute|Paintable hydrophobic and lubricant-infused surface coatings and processes for making and using same|EP3513962A4|2016-09-13|2019-10-23|Nissan Motor Co., Ltd.|Antifouling structure|
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    法律状态:
    2016-09-22| PLFP| Fee payment|Year of fee payment: 2 |
    2017-03-10| PLSC| Search report ready|Effective date: 20170310 |
    2017-09-19| PLFP| Fee payment|Year of fee payment: 3 |
    2018-09-18| PLFP| Fee payment|Year of fee payment: 4 |
    2019-09-25| PLFP| Fee payment|Year of fee payment: 5 |
    2020-09-30| PLFP| Fee payment|Year of fee payment: 6 |
    2021-09-30| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1558264A|FR3040700B1|2015-09-07|2015-09-07|GLAZING OF A TRANSPORT VEHICLE WITH FLAT AND DUST COATING ASSOCIATED WITH A DETECTION APPARATUS|FR1558264A| FR3040700B1|2015-09-07|2015-09-07|GLAZING OF A TRANSPORT VEHICLE WITH FLAT AND DUST COATING ASSOCIATED WITH A DETECTION APPARATUS|
    CA2995345A| CA2995345A1|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device|
    CN201680051727.XA| CN107949548A|2015-09-07|2016-09-06|The transport vehicle glass pane with waterproof and dustproof coating combined with detection device|
    MX2018002769A| MX2018002769A|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device.|
    BR112018002992-0A| BR112018002992A2|2015-09-07|2016-09-06|water-repellent, dust-repellent transport vehicle pane associated with a detection device|
    KR1020187009518A| KR20180050370A|2015-09-07|2016-09-06|Transport vehicle glazing with waterproof and dustproof coatings associated with detection devices|
    PT167757897T| PT3347320T|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device|
    EA201890651A| EA036028B1|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device|
    ES16775789T| ES2781872T3|2015-09-07|2016-09-06|Dust and water repellent coating transport vehicle glazing associated with a detection device|
    EP16775789.7A| EP3347320B1|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device|
    JP2018512286A| JP2018528925A|2015-09-07|2016-09-06|Vehicle glazing with water repellent and dust proof coating associated with the detection device|
    PL16775789T| PL3347320T3|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device|
    PCT/FR2016/052208| WO2017042469A1|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device|
    US15/757,606| US10508054B2|2015-09-07|2016-09-06|Transport vehicle glazing with water repellent and anti-dust coating associated with a detection device|
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