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
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/62—Plasma-deposition of organic layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
  • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
• • 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
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/001—General methods for coating; Devices therefor
  • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45595—Atmospheric CVD gas inlets with no enclosed reaction chamber
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
  • C23C16/505—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using radio frequency discharges
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2203/00—Other substrates
  • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2203/00—Other substrates
  • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
  • B05D2203/35—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
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/76—Hydrophobic and oleophobic coatings
• • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/152—Deposition methods from the vapour phase by cvd
  • C03C2218/153—Deposition methods from the vapour phase by cvd by plasma-enhanced cvd
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T50/00—Aeronautics or air transport
  • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

• the present invention relates to the treatment of a substrate to render the surface hydrophobic / oleophobic.
• the substrate according to the invention consists in particular of a glass material, a ceramic, or a glass-ceramic.
• the glazings according to the invention are, for example, glass panes. They are used, in particular, in the aeronautical, railway or automobile field. They can also be used in the field of building or in the field of interior design such as, for example, decorative panels, for furniture, appliances (doors of refrigerators, ovens, showcases) and so on.
• This type of treatment aims in a known manner to give the substrate the "hydrophobic" character, for example to provide a rain-proofing feature, and / or an oleophobic character, for example to provide an "easy-to-clean" or antigraffiti functionality .
• Wettability refers to the property that polar or non-polar liquids adhere to the substrate and form an annoying film, as well as the tendency of a substrate to retain dust or dirt of any kind, fingerprints, insects, etc. .
• hydrophobicity / oleophobia The property of non-wettability of a substrate, more commonly referred to as hydrophobicity / oleophobia, is even higher when the contact angles between a hydrophilic or oleophilic liquid and this substrate are high, for example at least 90 ° for the water. The liquid then tends to flow easily, in the form of drops, onto the substrate, by simple gravity if the substrate is inclined, or under the effect of aerodynamic forces in the case of a moving vehicle.
• Known agents for imparting this hydrophobicity / oleophobicity property are, for example, fluorinated alkylsilanes as described in patent applications EP 0 492 417, EP 0 492 545 and EP 0 672 779.
• this layer can be obtained applying to the surface of a substrate a solution containing fluorinated organosilanes in a nonaqueous organic solvent.
• a nonaqueous organic solvent EP 0 492 545 cites, in particular, n-hexadecane, toluene, xylene, etc. These solvents are particularly suitable for a fluorinated chlorosilane. It is also possible, according to this document, to use a methyl or ethyl alcohol as a solvent when the fluorinated silane is a fluorinated alkoxysilane.
• hydrophobic / oleophobic agents are, in particular, alkylsilanes whose alkyl group has at least one perfluorinated end, that is to say consisting of a group F3C- (CF2) n -, in which n is a whole number positive or zero.
• F3C- (CF2) n - perfluorinated hydrocarbons as suitable solvents.
• Other hydrophobic / oleophobic agents are also known, such as those described in application US 2004/247886.
• Patent EP 799873 more particularly describes liquid-developed rain coatings comprising a silica-based underlayer obtained from a precursor of the Si (OEt) 4 or SiCl 4 type and a functional layer based on silica. perfluoroalkylsilane.
• EP 1 102 825 discloses a composition for a hydrophobic / oleophobic coating incorporating both a fluorinated alkylsilane and a disilane, said composition being applied to an underlayer of the previously described type.
• the deposit techniques used can be of different natures. The most common is the application of the material constituting the hydrophobic / oleophobic layer or the underlayer (or more often a precursor thereof) via a soaked wipe. This technique is well known in the art as ragging. In general, the material or its precursor is provided on the surface of the substrate via a dilute water / alcohol solution further comprising a catalyst system incorporating the mixture of an alcohol and an acid as described. in the application JP 5-31 1 156.
• liquid deposition techniques are also known, which make it possible to obtain coatings of substantially identical quality, in particular spraying techniques (a process often called “spray-coating” ) as described in the application EP 545 201 A2, which also allow better control of the thickness of the layers, or centrifugation techniques, according to methods known in the art by the term spin-coating, soaking (processes often called dip-coating) or watering (processes often called flow-coating).
• the Applicant has proposed in a first way, in WO2005 / 118501 or WO2005 / 084943, to deposit an underlayer in the form of metal oxides in a thin layer on the support, then to subject this thin layer to an excitation operation of the underlayer by a plasma, which can go until an engraving, to make the surface rough.
• the hydrophobic coating is then applied to the roughened surface. In this way it has been obtained very good performance both in terms of the mechanical strength of the coating hydrophobic, at the level of its chemical behavior, in the sense previously described.
• the described method makes it possible to obtain at low cost thin films whose mechanical properties are greater than those obtained by conventional liquid application techniques.
• This application does not deal with the problem of the chemical resistance of the hydrophobic layers thus formed, in particular in the case where a glass substrate is used.
• the hydrolytic resistance of the material conditions its potential applications, especially outdoors.
• the main subject of the present invention is thus coatings resistant not only to friction and UV radiation but also having a high chemical resistance, that is to say, typically allowing them to fulfill the specifications imposed by the present time by the automotive industry, both in terms of resistance to friction, UV and climatic sustainability.
• the coatings according to the invention also have performances substantially equal to those of the coatings known at this date with regard to the other specifications necessary for their various uses such as, for example, the initial contact angle to the water and the volume. drop of drops.
• the present invention relates, in a first aspect, to a method for synthesizing a hydrophobic coating on a glass, ceramic or glass-ceramic substrate, preferably glass, by bringing said substrate into contact with a mixture of a gas excited, derived from a device generating a plasma substantially at atmospheric pressure and a gas containing at least one fluorinated organic compound, said method being characterized in that a sub-layer, preferably mineral, the thickness of which is between 1 and 100 nm is previously deposited on said substrate. From an economic and technical point of view, the thinnest sub-layers, that is to say those whose thickness is typically between 5 and 50 nm, or even between 10 and 30 nm, are preferred according to 'invention.
• the precursor fluorinated compound of the hydrophobic layer may be chosen from all the compounds known for this purpose at present.
• the precursor may be selected according to the invention from the following compounds: perfluorinated silanes, polyetherperfluorosilanes, mixtures including a fluorocarbon and a precursor of silicon or other metal chosen from group Al , Ga, Sn, Ti, Ta, Cr, Z, Nb, In, Fe, Co, V, Y.
• the sub-layer consists of at least one inorganic compound included in the group consisting of metal oxides, nitrides, carbides, or oxy carbides or oxynitrides.
• the sub-layer consists of an inorganic compound selected from the group consisting of SiO 2, Al 2 O 3 , Ga 2 O 3 , SnO 2 , TiO 2 , Ta 2 O 5 , Cr 2 O 3 , ZrO 2 , Nb 2 O 5 , In 2 O 3 , Fe 2 O 3 , CoO 3 , V 2 O 5 , Y 2 O 3 , TiN, SiO x with x less than 2, SiO p C q or SiO p N q with p between 1 and 2, and q .
• the inorganic compound is optionally doped so as to make it an electronic and / or ionic conductor or in order to improve its hydrolytic resistance or in such a way as to modify its optical properties.
• the underlayer may be deposited by means of a device generating a plasma substantially at atmospheric pressure.
• the sublayer may be deposited by magnetron sputtering, by thermal CVD or by low-pressure plasma or by sol-gel.
• the fluorinated compound is a fluorinated organometallic compound of formula:
• Ri to RO represents hydrogen or groups comprising at least one carbon atom, at least one of the groups Ri to RO comprising fluorine.
• the fluorinated compound is a fluorinated silane of formula:
• R is a fluorocarbon chain
• A is a chain fluorocarbon which may be interrupted by ether groups -O- or thioether -S-
• Z is a linking group between the fluorinated chain and the silane such as a carbon chain
• X is a halogen, preferably Cl or I, or a alkoxy group and R 'is an alkyl group or a hydrogen atom, n being between 0 and 5 and p being between 0 and 3.
• the fluorinated compound is a perfluoroalkylsilane of formula:
• m 0 to 15, preferably 5 to 9;
• p 0, 1 or 2, preferably 0 or 1, very preferably 0;
• R ' is an alkyl group or a hydrogen atom
• X is a hydrolyzable group such as a C1-type halide group or an alkoxy group.
• the fluorinated compound is a fluorocarbon precursor comprising only C, H and F, of the saturated type corresponding to the formula C n F2n + 2 or of the unsaturated type corresponding to the formula C n F2n or of the fluoroether type having the formula C n F2nO, n being an integer ranging from 1 to 20.
• the gas contains a mixture of at least one fluorinated compound as previously described, in particular the preceding fluorocarbon compound, and at least one precursor, preferably chosen from organometallic compounds, organosilicon compounds or halides, of a element included in the group consisting of Si, Al, Ti, Sn, Zr.
• at least one fluorinated compound as previously described, in particular the preceding fluorocarbon compound
• at least one precursor preferably chosen from organometallic compounds, organosilicon compounds or halides, of a element included in the group consisting of Si, Al, Ti, Sn, Zr.
• Another object of the invention is a product whose outer surface, most often constituted by a glass, ceramic, glass-ceramic or natural mineral material, is provided at least in part with a hydrophobic / oleophobic coating obtained from a method as previously described.
• the product of the invention is for example a monolithic glazing, laminated or multiple. It is specified that we mean:
• “Monolithic glazing” means glazing consisting of a single sheet of glass
• laminated glazing a stack of several sheets integral with each other, for example sheets of glass or plastic fixed to each other by means of adhesive layers of polyvinyl butyral, polyurethane ...;
• multi glazing an assembly of disjointed sheets, that is to say, in particular separated from each other by layers of air.
• hydrophobic / oleophobic coating of the invention allows the flow of drops of water or other liquid on vertical or inclined surfaces, possibly under the effect of aerodynamic forces for example in the case of a moving vehicle.
• these flowing drops include dirt and drag them.
• the visibility through the glazing is improved to a degree that we can dispense in some cases cleaning devices (windshield wipers, windshield wipers).
• the invention also relates to the applications of the product: - as glazing for transport vehicle (automobile side windows, train, bus, aviation windshield or automobile) or for the building;
• a furniture element especially as a mirror, storage shelf, tablet for household appliances such as a refrigerator, a shower cubicle element, partition, tables, doors, railings ...;
• - as a screen, including television screen, computer screen, touch screen, plasma screen.
• FIG. 1 illustrates a preferred embodiment of the invention, although not limiting, in which an inorganic silica underlayer and the hydrophobic layer are both deposited by contacting a glass substrate with a mixture of a precursor of said layers and a gas previously excited in a plasma generated at atmospheric pressure.
• a so-called "out of equilibrium” or cold plasma plasma is preferably used, that is to say that the temperature of the gases is significantly lower than the electronic temperature within the plasma.
• the gas temperature is less than 300 0 C.
• the implementation mode shown in Figure 1 incorporates including the use of a device of known technology, generating a remote plasma in atmospheric nitrogen, often called in the field "dielectric barrier discharge" or DBD.
• the substrate may be flat or previously subjected to a shaping such as bending before the deposition of the hydrophobic coating.
• this embodiment of the invention uses an indirect plasma apparatus with 3 slots, a synoptic representation of which is given in FIG. 1.
• the fluorinated precursor of the hydrophobic layer is projected towards the substrate by means of the central slot January 1, the two outer slots 18, 18 'for the projection of two curtains of gas excited by plasma discharges generated upstream.
• the precursor is therefore in accordance with the invention mixed post discharge, that is to say placed in contact with the excited gas (plasma) downstream of the discharge areas.
• the means for generating the plasma consist of two pairs of parallel planar external electrodes 2 and internal 2 '.
• Each of the plane electrodes 2, 2 ' is covered with a dielectric material 3.
• the space between two electrodes 2 and 2' facing each other delimits volumes or zones respectively numbered 4 and 4 'in FIG.
• the dielectric is for example based on alumina, typically deposited by the technologies called plasma torch or plasma spray, but any other type of dielectric or deposition process can be used.
• the inter-electrode distance is in general between 0.5 and 10 mm, preferably between 1 and 3 mm, especially when the plasma gas is mainly composed of nitrogen.
• the external electrodes 2 are connected to a mass 5 and the internal electrodes 2 'are connected to the AC power supply 6, the opposite being also possible.
• a plasma is generated in a gas introduced at the zones 4 and 4 'by energizing the electrodes, at a frequency and an amplitude chosen according to the techniques of the art.
• the plasma slits are fed with plasma gas from a reservoir 7 and optionally additive stored in a container 8 by means of the gas lines 9.
• the gases are homogenized and distributed via the injection chambers 10, maintained in fluid communication with the zones 4, and 4 '.
• the fluorinated precursor, stored in a reservoir 12 is introduced via a gas line 13 into the injection chamber 14.
• the precursor may be either gaseous, liquid or solid. It is carried out by the traditional routes, in particular by bubbling if the precursor is liquid, or by vaporization in the case of a liquid or solid precursor dissolved in a solvent.
• the compound is mixed and homogenized in the chamber 14 with a dilution gas (not shown), whose composition is for example close to or identical to that of the plasma gas used to feed the chambers 10.
• the gas mixture (fluorinated compound and dilution gas) propagates in the volume 17 generated between the two pairs of electrodes 2, 2 'and is discharged through the injection slot 1 1, located between the two outlet slots 18, 18' of the discharge plasma generated respectively in zones 4 and 4 '.
• All of the gases are blown in a mixture towards the glass substrate 15 which passes under the device, thus allowing the contacting of the activated fluorinated organic compound and the deposition of the layer on said substrate.
• the distance 16 between the device and the substrate may be between 1 mm and 5 cm, preferably between 2 mm and 1 cm.
• the length of the slots 1 1, 18, 18 ' is advantageously equal to the width of the portion of the substrate on which the coating is to be deposited.
• the primer solution is obtained from a mixture of Si (OC 2 Hs) 4 at 0.3% by weight in a solution of 90% by weight of isopropanol and 10% by weight of a 0.3N aqueous HCl solution, during the first deposition step.
• the priming solution is then deposited by scraping on the air side of a soda-lime glass substrate marketed by Saint-Gobain Glass France under the brand name Planilux® and previously polished with the help of a solution of cerium oxide and then thoroughly rinsed with demineralised water.
• Planilux® a soda-lime glass substrate marketed by Saint-Gobain Glass France under the brand name Planilux® and previously polished with the help of a solution of cerium oxide and then thoroughly rinsed with demineralised water.
• the thickness of this layer thus obtained is between 5 and 10 nm.
• Deposition of the hydrophobic layer As soon as the deposition of the sublayer is complete, the perfluorodecyltriethoxysilane solution is in turn deposited. by the same crimping technique.
• the deposition of the different layers is carried out by the well-known technique of scraping, in which the material or its precursor is deposited via a soaked rag. After standing for 15 minutes at room temperature, the excess fluorosilane is removed by cleaning with a cloth soaked in isopropanol.
• EXAMPLE 2 (According to the Prior Art) The step of applying the hydrophobic layer of the preceding example is reproduced for the preparation of a second sample E2, but the Planilux® glass substrate is this time covered with a 100 nm layer of SiO 2 obtained by pyrolysis, according to the teachings of Example 3 of EP545201 A2 According to techniques identical to those of Example 1, a 3% solution of CF 3 (CF 2) 7 (CH 2) 2 Si ( OC 2 H 5) 3 in a mixture of 90% ethanol and 10% water, acidified with 0.3 N HCl is applied by the scouring technique to the substrate coated with the underlayer.
• a third sample E3 is prepared according to the teachings of the application WO2005 / 084943.
• Sample 3 is obtained by scouring a solution of fluorosilane on a SiO 2 sub-layer, of thickness 50 nm, according to the method described in Example 2 of WO2005 / 084943.
• This undercoat was previously deposited on the Planilux® glass substrate in a low pressure PECVD reactor then textured using a plasma at atmospheric pressure, in accordance with the procedure described in Example 2 of this disclosure.
• a fourth sample was prepared by direct deposition of a hydrophobic layer from the compound CF3 (CF2) 7 (CH2) 2Si (OC2Hs) 3 using the device illustrated in Figure 1 and scrolling the glass substrate Planilux® under said device.
• the width of the slots in the direction perpendicular to the direction of travel of the glass is 120mm.
• the power supply is a voltage power supply delivering a pulsed signal with a pulse duration of 5 ⁇ s and a repetition frequency of 18kHz.
• the glass is translated under the nozzle, with a speed of 0.5m / min.
• a fifth sample was prepared by depositing a hydrophobic layer from the compound CF3 (CF2) 7 (CH2) 2Si (OC2Hs) 3 using the device illustrated in FIG. 1 and scrolling the Planilux® glass substrate under said device.
• CF2 CF2
• CH2Si O2Hs
• a silica underlayer was this time previously deposited using an identical device before the deposition of the hydrophobic layer.
• the experimental conditions of the successive deposits of the underlayer and the hydrophobic layer are as follows:
• l st step depositing a sublayer of silica
• the deposit was made in this example from tetraethoxysilane (TEOS) and oxygen on a soda lime glass (SGG-Planilux @) with a plasma source of the type described in connection with Figure 1, 12cm wide dimension.
• TEOS tetraethoxysilane
• SGG-Planilux @ soda lime glass
• other precursors may be used, preferably chosen from organometallic compounds or halides, mixed with an oxidizing or reducing gas.
• Gas conditions - Plasma slits: the gas is a mixture of N2 and 1% volume of
• the glass is translated under the nozzle, with a speed of 0.5m / min.
• the feed is identical to that of Example 4.
• the layer obtained has a thickness of 50 nm, a density of 2.1 g / cm 3 , few carbon residues as shown by measurement with an electron microprobe apparatus very good adhesion to the glass (no delamination after 600 turns "Taber” abrasion test method, implemented according to ASTM D 1044-78 (CS-IOF grinding wheels, 500 gr load)).
• Step 2 deposition of the layer Hydrophobic
• Example 4 The previously treated glass (with the silica underlayer) runs under the same equipment as in Example 4.
• the deposition conditions are identical to those of Example 4.
• the glass is translated under the nozzle, with a speed of scrolling 0.5m / min.
• the feed is identical to that of Example 4.
• Example 5 the compounds, conditions and steps described in Example 5 were identical except for the speed of travel of the glass during the deposition of the silica underlayer: the glass is translated this time at 0.9 m / min. The thickness of the underlayer thus obtained is 28 nm.
• EXAMPLE 7 (According to the Invention)
• the compounds, conditions and steps described in Example 5 were identical except for the speed of travel of the glass during the deposition of the sub-component.
• silica layer the glass is translated this time to 2.5 m / min.
• the thickness of the underlayer thus obtained is 10 nm.
• Initial performance measurement The measurement of the initial contact angle of a drop of water and hexadecane, provides a reference indication of the hydrophobic or oleophobic nature of the grafted substrate, the hysteresis measurements (difference between the angle of advancement and the angle of recoil) and the volume necessary for the detachment of a drop, the substrate being inclined by 45 °, gives an indication of the performance of the glass when the vehicle is in motion (the speed required to pick up the drops are all the lower as the hysteresis and the volume of offset are low).
• Friction resistance obtained by measuring the residual contact angle of the water on the sample after the hydrophobic / oleophobic graft coating has undergone a Toyota ® friction test.
• the test is carried out according to standard TSR7503G, with a load of 0.3 kg / cm 2 over an area of 4 cm 2 , a translational speed of 40 cycles / minute and using a device manufactured by Daiei Kagaku Seiki.
• a test sample is considered satisfactory for side window applications if the contact angle remains greater than 80 ° after 1500 cycles (TSR7102G-5 standard). For applications as a windscreen, the contact angle must remain greater than 80 ° after 2500 cycles (standard TSR7102G-3).
• the friction test was continued up to 10,000 cycles, provided that the contact angle remains greater than 80 °. 3 °) the resistance to UV-A radiation is measured by a UV-wet test representing the climate of a humid country (for example Florida), according to the standard PV 3930.
• the test was carried out on a WOM Ci device 65 of the Atlas brand with an exposure of 0.6 W / m 2 for a wavelength of 340 nm, with a relative humidity of 60 to 80% and a temperature of 35 to 45 ° C. The exposure was in all cases 1000 hours.
• Examples E5 to E7 in accordance with the invention, are characterized by the combination of an underlayer and a hydrophobic / oleophobic layer deposited by means of an atmospheric plasma. , leads to initial properties of hydrophobicity / oleophobia generally better or at least substantially equal to those of the prior art.
• the samples according to the invention have besides these very good initial performance, very good weather resistance (BSN and wet UV test), mechanical (TOYOTA test). The combination of these three excellent properties is unknown to date.
• the El sample has acceptable initial properties and frictional resistance compared to the current automotive specifications for applications as side window but insufficient chemical resistance.
• Sample E2 has initial hydrophobic properties and mechanical strength similar to El with improved chemical resistance.
• Sample E3 if it has remarkable mechanical strength properties, much better than Examples E1 and E2 and compatible with use as an automotive windshield, with good weather durability properties, but it has the disadvantage a high hysteresis and drop drop volume higher than the other samples, reflecting a drop in initial functionality.
• the process used to produce the rough sub-layer is a complex (multi-step) and expensive process (deposition of the underlayer and its vacuum etching).
• Sample E4 has extremely high initial and mechanical properties (at least equal to E3) but a chemical resistance to the BSN and UV-wet test which is very insufficient.

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